JP3140829B2 - Insecticidal 1- (2-pyridyl) pyrazole - Google Patents

Abstract

Novel 1-(2-pyridyl)pyrazoles of formula (I) <CHEM> wherein: X is a halogen, nitro or unsubstituted or halo-substituted alkylsulfenyl, alkylsulfinyl or alkylsulfonyl, wherein the alkyl moiety is a linear or branched chain, containing one to four carbon atoms, and where substituted, is substituted by one of more halogen atoms, which are the same or different, up to full substitution of the alkyl moiety; Y is hydrogen, halogen, cyano, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, alkoxy, amino, alkylamino, dialkylamino, trialkylammonium salt, cyanoalkylamino, alkoxyalkylamino, alkoxycarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino, alkylaminocarbonylamino, dialkylaminocarbonylamino or alkoxyalkylideneimino, wherein the alkyl and alkoxy moieties are linear or branched and contain one to four carbon atoms, and the haloalkyl moieties are substituted by one or more halogen atoms, which are the same or different, up to full substitution of the alkyl moiety; Z is cyano or halogen; and R2, R3, R4 and R5 are each individually hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro, wherein the alkyl and alkoxy moieties are linear or branched and contain one to four carbon atoms, and the halo-substituted moieties are substituted by one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and alkoxy moieties; at least one of R2 to R5 being other then hydrogen. The invention further relates to intermediates and processes to make the compounds, pesticidal compositions comprising the compounds, and methods of use of the compounds for the control of arthropods (mites, aphids or insects) nematodes, helminths or protozoa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel 1- (2-pyridyl) pyrazoles, intermediates thereof and processes for producing these compounds. The present invention further relates to compositions and methods for controlling arthropods, nematodes, parasites or protozoan pests using said compounds. The invention particularly relates to the use of said compounds or compositions thereof, particularly in agriculture, as insecticides for controlling arthropods, especially aphids or leaf or soil insects, without harming the crops. .

Various 1- (substituted phenyl or pyridyl)
-A substituted pyrazole compound, a herbicide, a plant growth regulator,
It is known to exhibit various pesticidal activities, including activity as fungicides, insecticides and nematicides. Compounds of this type include the following: JP 63-313773 discloses as a herbicide and fungicide 1- (substituted-2-pyridyl) -5- (substituted) in which the 3-position of the pyrazole ring is unsubstituted. Amino) pyrazoles are disclosed.

[0003] JP 63-174905 discloses a pyrazole ring having a 3-pyrogenic ring as a plant growth regulator for thinning fruits.
Disclosed are unsubstituted or alkyl substituted 1- (substituted-2-pyridyl) -5- (substituted amino) pyrazoles.

US Pat. No. 4,772,312 discloses, as a herbicide, 1- (substituted-2-pyridyl) -5- (substituted amino) pyrazoles in which the 3-position of the pyrazole ring is unsubstituted or alkyl-substituted. It has been disclosed.

[0005] In GB 2,136,427, as a herbicide, 1- (substituted-), in which the 3-position of the pyrazole ring is unsubstituted.
2-Pyridyl) -5- (substituted amino) -4-cyanopyrazoles are disclosed.

The chemical literature J. Khan and Pinto.
Heterocyclic Chem. , 18 . 9-1
4 (1981) discloses 1- (substituted-2-pyridyl) pyrazoles in which the 3-position of the pyrazole ring is unsubstituted or substituted with methyl, phenyl or p-nitrophenyl. No specific activity is described.

[0007] EP 295,117 and WO 87
No. 03781 discloses 1- (substituted phenyl) pyrazoles for controlling arthropods, nematodes, parasites and protozoan pests.

[0008] US Pat. No. 4,804,675 discloses 1- (substituted-2) unsubstituted or alkyl- or haloalkyl-substituted 3-positions of the pyrazole ring as insecticides, acaricides and nematocides. -Pyridyl) -5- (substituted amino) pyrazoles are disclosed.

JP 2142-785 discloses, as a herbicide, 1- (substituted-2) in which the 3-position of the pyrazole ring is unsubstituted.
-Pyridyl) -4-chloro-5- (substituted amino) pyrazoles are disclosed.

In EP 284,030, as a herbicide, 1- (substituted-2) in which the 3-position of the pyrazole ring is unsubstituted.
-Pyridyl) -4-nitro-5- (substituted alkoxy) pyrazoles are disclosed.

US Pat. No. 4,770,692 discloses that as a herbicide and a plant growth regulator, a pyrazole ring is unsubstituted or substituted with alkyl or haloalkyl at the 3-position and various substituents are substituted at the 5-position. Having 1- (substitution-2
-Pyridyl) -4-nitro- (or cyano-) pyrazole is disclosed.

EP 249,033 discloses that as a pesticide, an acaricide and a nematocide, the 3-position of the pyrazole ring is substituted with hydrogen, alkyl or haloalkyl.
Disclosed are 1- (substituted-2-pyridyl) pyrazoles in which the position is substituted with alkylthio or its oxidized state and the position 5 is substituted with alkoxy or alkylthio.

US Pat. No. 4,918,085 discloses 1- (substituted phenyl) -5-alkoxy-3-cyano-5 as compounds for controlling arthropods, nematodes, parasites and protozoan pests. Sulfenylalkylpyrazoles are disclosed.

Thus, a wide variety of different types of biological activities can be obtained depending on the types and positions of the substituents on the pyrazole ring, but the type and degree of the activities are not obvious.

The present invention relates to novel 1- (substituted-2-pyridyl) pyrazole compounds which exhibit unexpectedly excellent insecticidal properties, especially as insecticides (especially aphid insecticides) or acaricides.

Compounds of this kind, including isomers such as diastereoisomers and optical isomers, have the general formula (I)

[0017]

Embedded image [Wherein X represents halogen, nitro, unsubstituted or halo-substituted alkylsulfenyl, alkylsulfinyl or alkylsulfonyl, wherein the alkyl moiety is a straight or branched chain having 1 to 4 carbon atoms, and Consists of one or more halogen atoms which are the same or different from each other up to complete substitution of the alkyl moiety, and Y is hydrogen, halogen, cyano, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, alkoxy, amino, alkylamino, Dialkylamino, trialkylammonium salt, cyanoalkylamino, alkoxyalkylamino, alkoxycarbonylamino, alkylcarbonylamino, haloalkylcarbonylamino,
Alkylaminocarbonylamino, dialkylaminocarbonylamino or alkoxyalkylideneimino, wherein the alkyl and alkoxy moieties are linear or branched having 1 to 4 carbon atoms, and the range from when halo substitution leads to complete substitution of the alkyl moiety And Z is cyano or halogen, and R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy , Cyano or nitro, wherein the alkyl and alkoxy moieties are straight-chain or branched having 1 to 4 carbon atoms, and the same or different ones from each other in a range in which halo substitution leads to complete substitution of the alkyl and alkoxy moieties. consists or more halogen atoms, provided that at least one hydrogen or more of R ₂ to R ₅ A compound or an acid addition salt thereof represented by the a] ones.

[0018] Insecticidal compounds of the present invention, in a preferred embodiment, the following X represents S (O) nR ₁ formula (II)

[0019]

Embedded image Selected from the compounds represented by

In the above formula, Y is hydrogen, halogen, cyano,
Alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, alkoxy, amino, alkylamino,
Dialkylamino, a trialkylammonium salt, a cyanoalkylamino, an alkoxyalkylamino, an alkoxycarbonylamino, an alkylcarbonylamino, a haloalkylcarbonylamino, an alkylaminocarbonylamino, a dialkylaminocarbonylamino or an alkoxyalkylideneimino, wherein the alkyl and the alkoxy moiety are carbon atoms A straight or branched chain having 1 to 4 atoms,
Halo substitution consists mutually the same or different one or more halogen atoms in the range up to full substitution of the alkyl moiety, R ₁ is the same as each other or different from one or more in the range up to the alkyl group is fully substituted Represents a straight-chain or branched-chain alkyl having 1 to 4 carbon atoms substituted by a halogen atom, wherein n is 0, 1 or 2, and R ₂ and R ₄ are each independently hydrogen, halogen, alkyl, Represents haloalkyl, alkoxy, haloalkoxy, cyano or nitro, in which the alkyl and alkoxy moieties are straight or branched having 1 to 4 carbon atoms, and the halo substitution extends to the complete substitution of the alkyl and alkoxy moieties. Same or different 1
Consisting of one or more halogen atoms, provided that at least one of R ₂ and R ₄ is other than hydrogen. Further preferred compounds of formula (II) are represented by formula (IIa).

In this formula, Y represents amino, alkylamino, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, alkoxyalkylamino, alkylcarbonylamino, haloalkylcarbonylamino or alkoxyalkylideneimino, wherein the alkyl and alkoxy moieties have carbon atoms. 1-4 straight or branched chains, consisting of one or more halogen atoms which are the same or different from each other up to the point where halo substitution leads to complete substitution of the alkyl moiety, wherein R ₁ and n are of the formula (II) Wherein R ₂ is hydrogen or halogen, R ₄ represents hydrogen, halogen, haloalkyl or haloalkoxy, and the alkyl and alkoxy moieties are straight or branched having 1 to 4 carbon atoms. Until the halo substitution leads to the complete substitution of the alkyl and alkoxy moieties. Made of the same or different one or more halogen atoms each other in the range of, provided that at least one of R ₂ and R ₄ is other than hydrogen.

Further preferred specific compounds are those of the formula (IIb)
Indicated by

In this formula, Y represents amino, alkylamino, alkoxymethylamino or alkoxyalkylideneimino, the alkyl and alkoxy moieties contain one or two carbon atoms, and R ₁ is trifluoromethyl, dichlorofluoromethyl or Represents chlorodifluoromethyl, n is 0, 1 or 2, R ₂ is bromine, chlorine or fluorine, and R ₄ is bromine, chlorine, fluorine, trifluoromethyl or trifluoromethoxy.

In one particular embodiment of the invention, Y in formula (I) is amino. Such compounds are referred to as compounds of formula (Ia).

Formula (II) described in Examples 1-27 described below
Some of the preferred compounds are listed by the following identification categories: Good to excellent aphid control activity: Examples 1, 2, 3, 5, 6, 8, 9, 10, 14, 1
Compounds of 8, 20, 21 and 26.

Those having good to excellent aphid control activity and a broad spectrum of insecticidal activity: Examples 1, 2, 3, 5, 6, 8, 9, 10, 14 and 1
Compound of 8.

Those showing good insecticidal activity against cereal (rice) pests: The compounds of Examples 1, 2, 5, 10 and 18.

Those exhibiting good insecticidal activity against soil insects: The compounds of Examples 6, 10 and 18.

Absorbs from roots and is permeable (transferable, systememi) to leaf pests (especially insects or aphids)
c) Insecticidal activity: compounds of Examples 2, 3, 9, 10, 14 and 21.

An object of the present invention is to provide a novel 1- (2-pyridyl) pyrazole compound, a method for producing the same and an intermediate thereof.

A second object of the present invention is to provide, for example, agronomically or pharmaceutically acceptable compositions.

A third object of the present invention is to provide highly active compounds for use against arthropods, especially aphids or insects, plant nematodes, or parasites or protozoan pests. Compounds of this kind are advantageously used, for example, in agricultural or horticultural crops, forestry, veterinary medicine or livestock raising, or in public health.

A fourth object of the present invention is to apply a broad spectrum of activity as an insecticide, acaricide or nematicide, including by osmotic action, by application to soil or leaves or treatment of seeds. The object is to provide the compounds shown.

It is yet another object of the present invention to provide compounds which have a strong activity through osmotic action, especially against sucking insect species, especially cereal pests or aphid species.

The above and other objects of the present invention will be readily apparent from the detailed description of the present invention.

Synthetic Methods or Processes The compounds of the general formula (I) can be prepared by known methods, ie by using pyrazole rings and, if necessary, modifying the substituents (ie those which have been used previously or have been used in the chemical literature). ) Can be produced by applying or adapting the method described in In the following description of the method, it is also understood that the order of introducing the various groups on the pyrazole ring can be performed in a different order, and that appropriate protecting groups can be required as known to those skilled in the art. I want to. Further, the compound of the general formula (I) can be converted to another compound of the general formula (I) by a known method.

If the symbols appearing in the formulas in the following description of the method are not specifically defined, they will be referred to as “before defined herein before” according to the first definition of each symbol in this specification. Yes "is to be understood. The term "protecting" refers to conversion to a suitable non-reactive group, which can be reconverted when desired, and to functional groups.
adding a group that renders y) unreactive. Within the definition of a method, unless otherwise stated, amino refers to an unsubstituted amino group.

The present invention includes certain intermediate compounds that are effective in preparing some of the compounds of interest herein. Such preferred intermediate compounds prepared as described herein are defined in the following manner.
Particularly more preferred intermediate compounds are those of the formula (II) as defined by formula (I) of the invention, or wherein R ₃ and R ₄ are each hydrogen or particularly preferred R ₂ and R ₄ are defined. R _{2 to} R as defined by
₅

The 1- (2-pyridyl) pyrazole of the present invention can be produced by various different methods. According to a preferred method of synthesis, compounds of the present invention, first, M is an alkyl 2-oxo-3-cyanopropionate 2 obtained by acid neutralization of the enolate salt 1 corresponding a metal cation, the appropriately substituted It can be obtained from intermediate product 4 by cyclization with 2-pyridylhydrazine 3 and subsequent further substitution or derivation. R is C
_An effective and novel intermediate 1- (substituted-2-pyridyl)-, which is _1-4 lower alkyl, preferably methyl or ethyl, and wherein R _{2 to} R ₅ are as defined in formula (I).
The formation of 3-alkoxycarbonyl-5-aminopyrazole 4 is as shown below.

Both starting materials 1 and 3 are commercially available or can be prepared according to known literature methods familiar to those skilled in the art. The aqueous solution of enolate salt 1 is first acidified with an inorganic acid such as sulfuric acid. The intermediate product 2 is then extracted in an inorganic solvent, which is added to a solution of 2-pyridylhydrazine 3 in a lower (C _1-4 ) alkyl alcohol such as methanol or ethanol. After forming the intermediate hydrazine in situ, a base such as sodium bicarbonate, which catalyzes the cyclization in situ, is added to give 1- (2-
(Pyridyl) pyrazole 4 is produced.

[0041]

Embedded image The compounds of the formula (I) according to the invention have various substituents, in particular X,
It is prepared by reacting a compound of formula 4 according to the method described below which introduces Y and Z.

The particularly useful novel intermediate 2-pyridylpyrazole compounds discussed in the process herein for preparing the compounds of formula (I) of the present invention are, inter alia, intermediates defined as follows: A compound of formula 4 , 9 or 10 corresponding to the compound of formula (III), a compound of formula 5 , 6 , 11 or 12 corresponding to the compound of intermediate formula (IV) and a compound of formula (V): a )

[0043]

Embedded image Wherein Z is C _1-4 alkoxycarbonyl, aminocarbonyl or cyano, and R ₂ , R ₃ , R ₄ and R
₅ are each independently hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro, provided that at least one of R _{2 to} R ₅ is not hydrogen, wherein the alkyl and alkoxy moieties are 1 to 5; 4
Straight or branched containing two carbon atoms, and halo substitutions are made up of one or more halogen atoms, the same or different, to the extent that the alkyl and alkoxy moieties are fully substituted)]; b)

[0044]

Embedded image Wherein Z is C _1-4 alkoxycarbonyl or aminocarbonyl, and X is halogen, nitro, or unsubstituted or halo-substituted alkylsulfenyl, alkylsulfinyl or alkylsulfonyl, wherein the alkyl moiety is 1 to 4 a linear or branched chain containing carbon atoms, halo substitution, to the extent that the alkyl moiety is fully substituted, the same or are composed of different one or more halogen atoms), R _2, R ₃ , R ₄ and R ₅ are each individually hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro (where alkyl is the proviso that at least one of R _{2 to} R ₅ is not hydrogen). And the alkoxy moiety is straight or branched containing 1 to 4 carbon atoms, and the halo substitution is alkyl and And to the extent that the alkoxy moiety is completely substituted) (consisting of one or more halogen atoms); and c)

[0045]

Embedded image [Wherein, Y, Z, R ₂ , R ₃ , R ₄ and R ₅ represent the formula (I)
As defined in

In particular, the more preferred compounds of the formula (I) of the present invention 4-sulfenated 1- (substituted-2-pyridyl) pyrazoles [X = S (O) _n R ₁ , where n and R ₁ are already defined Can be produced by various methods. Two preferred methods are described in Scheme 1, Scheme A
And B.

[0047]

Embedded image

[0048]

Embedded image Method 1 X is an alkylsulfenyl, haloalkylsulfenyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, Y is amino, Z is cyano, R ₂ ,
A compound of general formula (I), wherein R ₃ , R ₄ and R ₅ are as defined in general formula (I), and further a compound of formula (Ia) as defined subsequently, in particular a compound of formula 7 or 8 Is X
Is hydrogen, Y is amino, Z is alkoxycarbonyl, and R _{2 to} R ₅ are as defined from the intermediate of formula 4 by the process described in Scheme 1, Routes A and B It is manufactured as follows.

A) In Route A of Scheme 1, 3-A
Lucoxycarbonyl-5-aminopyrazole intermediate4
Is an alkyl or haloalkylsulfenyl halogen
Compound R₁SHALO (where R₁Is as defined above.
Alkyl or haloalkyl, with Halo being preferred
Is chlorine), and X is SR₁Expression that is5of
Obtain the intermediate. The reaction involves chlorinated hydrocarbons, hydrocarbons,
In inert aprotic organic solvents such as
In dichloromethane, optionally pyridine, tertiary
Acid acceptors such as secondary amines or alkali metal carbonates
It is convenient to use it. The reaction is a halogenated sulf
About -25 ° C to about 25 ° C depending on the boiling point of the phenyl reagent or solvent.
Performed between 100 ° C. Alternatively, sulfenylation can be performed on ice
Carried out at about 5 ° C. to about 100 ° C. in an organic acid such as acetic acid
You.

Intermediate carboxamide 6 is prepared from intermediate ester 5
Is reacted with ammonia in an inert organic solvent in the presence of a Lewis acid catalyst such as trimethylaluminum at a temperature of about -78 ° C to about 50 ° C. Alternatively, the intermediate ester 5 is hydrolyzed to the corresponding acid, which is then converted to the acid chloride by known chemical reactions,
This is further reacted with ammonia to obtain intermediate carboxamide 6 .

The intermediate carboxamide 6 is then converted, typically in a solvent such as phosphorus oxychloride or phosphorus pentoxide, optionally in an inert organic solvent, typically from about 30 ° C to about 180 ° C. Dehydrate to nitrile 7 at the reflux temperature of the solvent in ° C.

The oxidation of sulfide 7 to give sulfoxide (n = 1) or sulfone (n = 2) 8 can be carried out, for example, by using a suitable amount of peracetic acid, trifluoroperacetic acid, m.
Performed using chloroperbenzoic acid, hydrogen peroxide, a blend of peracetic acid and hydrogen peroxide, or potassium peroxy-sulfate commercially available as Oxone®. The reaction is usually carried out in an inert organic solvent, typically at about -3.
Performed at 0 ° C to about 180 ° C.

[0053] In another route B of Scheme 1 is a path, converts the intermediate ester 4 by reacting at ambient temperature with a base and an alkyl alcohol, such as ammonium hydroxide, first, the intermediate ester 4 to the intermediate carboxamide 9 I do. The resulting intermediate carboxamide 9 was converted to
Dehydrate to intermediate nitrile 10 as described in the conversion of 6 to 7 . Optionally dehydration from 9 to 10 can be accomplished by combining an anhydride such as trifluoroacetic anhydride and an organic base such as pyridine in an inert organic solvent such as dioxane or tetrahydrofuran at about -30C to about 100C. Performed using temperature.

The sulfenylation of the nitriles 10 to 7 is carried out as described in the conversion of compounds 4 to 5 in route A.

The sulfenyl compound 7 is oxidized as described above to produce 8 .

Method II X is halogen or nitro, Y is amino (or protected amino), Z is cyano, and R is C _1-4
A compound of general formula (I) wherein R ₂ , R ₃ , R ₄ and R ₅ are lower alkyl, as defined in formula (I), followed by a compound of formula (Ia) Especially the formula
The compound of 13 is prepared by directly halogenating or nitrating the intermediate compound of formula 4 as defined above, followed by amidation and dehydration according to the following method.

[0057]

Embedded image a) First, the intermediate compound of formula 4 wherein X is hydrogen is reacted with sulfuryl chloride, thionyl chloride, N-halosuccinimide, chlorine or bromine, optionally using an acid acceptor such as a Lewis acid or a catalyst. This gives an intermediate compound of formula 11 wherein X is halogen. The reaction is carried out in an inert aprotic organic solvent such as a chlorinated hydrocarbon, ether or acetonitrile. The reaction is carried out at a temperature of about -50 ° C to about 150 ° C, preferably about -10 ° C to about 50 ° C, depending on the reactivity of the pyrazole and the reactivity of the halogenating agent used.
Performed at about 110 ° C.

B) First, an intermediate compound of formula 4 wherein X is hydrogen is prepared by mixing a mixture of concentrated nitric acid and sulfuric acid in acetic acid or acetic anhydride, nitric pentoxide in a halogenated alkane, an ester of nitric acid such as ethyl nitrate, Using a nitrating agent such as a mixed anhydride such as acetyl nitrate or a nitrile halide and optionally a Friedel-Crafts catalyst such as ferric chloride or methyl nitrate or a nitronium salt such as nitronium tetrafluoroborate. The reaction gives an intermediate compound of formula 11 wherein X is nitro. The reaction is carried out in a suitable solvent such as acetic acid, acetic anhydride, tetramethylene sulfone, tetrahydrofuran or water, under neutral, basic or acidic conditions, at a reaction temperature of about -50C to about 155C. The preferred working procedure is
Nitration using nitrile chloride at a reaction temperature of about -10C to about 25C in the presence of titanium tetrachloride in tetramethylene sulfone.

C) Amidating the alkoxycarbonyl group to a carboxamide group according to the method described in the conversion of 5 to 6 in method Ia, the intermediate compound of formula 11 wherein X is halogen or nitro is converted to a compound of formula 1
Converted to intermediate compound 2 .

D) dehydration of the intermediate compound of formula 12 according to the method described in the conversion of 6 to 7 in method Ia, whereby formula 1 wherein X is halogen or nitro
3 to produce the compound of formula (Ia).

Method III Z is halogen and Y is amino (or protected amino)
R is C _1-4 lower alkyl, X, R ₂ ,
Compounds of the general formula (I) wherein R ₃ , R ₄ and R ₅ are as defined in the general formula (I), furthermore compounds of the formula (Ia) as defined subsequently, in particular compounds of the formula 16 or 16a Is such that Z is alkoxycarbonyl, X is alkylsulfenyl or haloalkylsulfenyl, and Y is
From an intermediate compound of formula 5 from method Ia wherein is amino
Or from an intermediate compound of formula 11 from method IIa where X is halogen or nitro, Z is alkoxycarbonyl and Y is amino, according to the following method.

[0062]

Embedded image a) hydrolyzing an intermediate compound of formula 5 or 11 (ie an ester) wherein Z is an alkoxycarbonyl in the presence of an acidic or basic catalyst according to well-known literature methods;
An intermediate compound of formula 14 where Z is carboxy is obtained.

B) First, the intermediate compound of the formula 14 in which Y is amino (or protected amino if necessary) is converted into the dry silver salt intermediate compound of the formula 15 , which is reacted according to the Hunsdeaker reaction to obtain Z Formula 16 wherein is a halogen,
That is, the compound of the formula (Ia) is obtained. The reaction is carried out in a halogen, especially bromine, in an inert organic solvent such as carbon tetrachloride for about 50 minutes.
The reaction is carried out at a reaction temperature of from about 200C to about 200C.

C) optionally the oxidation of a compound of formula 16 wherein X is an alkylsulphenyl or a haloalkylsulphenyl (sulfide, n = 0) as described for the conversion of 7 to 8 in method Ia Oxidation by the method affords the corresponding sulfinyl of formula 16a (sulfoxide,
n = 1) or sulfonyl (sulfone, n = 2) analogs.

Method IV The amino derivative Y is alkylamino, dialkylamino,
Trialkylammonium salt, cyanoalkylamino,
An alkoxyalkylamino, an alkoxycarbonylamino, an alkylcarbonylamino, a haloalkylcarbonylamino, an alkylaminocarbonylamino, a dialkylaminocarbonylamino or an alkoxyalkylideneimino, wherein X, Z, R ₂ , R ₃ , R ₄ and R ₅ have the general formula General formula (I) as defined in (I)
Or a compound of formula 17 or (Ib)
Is an amino and the other substituents are as defined, prepared by appropriate derivation of a compound of formula (Ia) corresponding to a compound of formula 7 , 8 , 13 , 16 or 16a .

In general, the derivation of compounds of formula (Ia) where Y is amino can be achieved, for example, by a suitable substituted alkyl halide (eg, where the halide is Cl, Br or I) or a suitable substituted acyl halide (eg, (Alkyl chloride) in an inert organic solvent, optionally in the presence of a base such as an acid acceptor or a catalyst. The reaction is carried out according to standard literature methods, usually at a temperature from about 0 ° C. to about 100 ° C., depending on the nature of the solvent and the alkylating or acylating agent used. A typical method is as follows.

[0067]

Embedded image a) Compounds of formula 17 or (Ib) in which the amino derivative Y is an alkylamino, dialkylamino, trialkylammonium salt, cyanoalkylamino or alkoxyalkylamino, may be substituted with a suitable unsubstituted or substituted alkyl iodide or dialkyl sulfate. A substituted alkylating agent,
Monoalkylation using an inert solvent such as acetonitrile, teratohydrofuran or dimethoxyethane at a reaction temperature of about 0 ° C to about 160 ° C, optionally in the presence of a base such as potassium carbonate or triethylamine. , Dialkylated and trialkylated. Alternatively, for methylation, the desired N-methylation is achieved using an Eschweiler-Clark reaction. This reductive methylation can be conveniently carried out by reacting an amine of formula (Ia), ie of formulas 7 , 8 , 13 , 16 or 16a , with formaldehyde and formic acid. This method is described in Clark et.
al, J.M. Am. Chem. Soc. , 55 , 457
As reported by US Pat. No. 1,1933.

B) Formula 1 wherein the amino derivative Y is alkylcarbonylamino or haloalkylcarbonylamino
7 or a compound of formula (Ib) wherein Y is amino
a), i.e. from a compound of formula 7 , 8 , 13 , 16 or 16a , which is combined with a suitable alkyl or haloalkylcarbonyl halide such as acetyl chloride or chloroacetyl chloride in a suitable organic solvent such as dichloromethane, ethyl ether or tetrahydrofuran. And, optionally, in the presence of an acid acceptor such as pyridine or triethylamine at a reaction temperature of about -10 ° C to about 100 ° C, preferably about -10 ° C to about 50 ° C.

C) Compounds of formula 17 or formula (Ib) in which the amino derivative Y is alkoxycarbonylamino, alkylaminocarbonylamino or dialkylaminocarbonylamino are obtained by reacting a compound of formula (Ia) in which Y is amino, ie, formulas 7 and 8 first be converted to its corresponding chloro carbonylamino or isocyanate intermediate product by treating a 13, 16 or 1 6a of the compound with phosgene
It is conveniently manufactured by a two-step method comprising the steps of: The reaction is carried out in an inert organic solvent such as toluene, dichloromethane or tetrahydrofuran at about -15 ° C.
It is carried out at a temperature from about 100C to about 100C, preferably from about -15C to about 50C. In a second step, the chlorocarbonylamino or isocyanate intermediate compound is reacted with a suitable alkyl alcohol, alkylamine or dialkylamine. This reaction involves halogenated alkanes,
It is carried out in an inert organic solvent such as toluene, ether or tetrahydrofuran at a temperature of about -20C to about 100C, preferably about 0C to about 50C, optionally in the presence of a base such as amino. .

D) Compounds of formula 17 or (Ib) in which the amino derivative Y is an alkoxyalkylidene imino,
Of formula (Ia) wherein is an amino, ie, of formulas 7 , 8 , 13 , 16
Alternatively, it is produced by reacting the compound of 16a with an appropriate alkyl orthoformate. The catalyst used is generally an inorganic acid such as hydrochloric acid or an organic acid such as p-toluenesulfonic acid. The reaction is performed at about -20 ° C to about 180 ° C.
C., preferably from about 0.degree. C. to about 120.degree. C., in the presence of an inert organic solvent such as a hydrocarbon, chlorinated hydrocarbon, aromatic, ether, alcohol, and the like. Also, the alkyl orthoformate itself can be used as a solvent.

Method V Y _sub is hydrogen, halogen, cyano, alkylsulfenyl, alkylsulfinyl or alkylsulfonyl, and X, Z, R ₂ , R ₃ , R ₄ and R ₅ are defined in general formula (I) Compounds of formula (I), furthermore compounds of formula (Ic), and especially compounds of formula 18 , are of formula (Ia) wherein the substituents are as defined, i.e.
It is produced by deamination or substitution deamination of the compound of 7 , 8 , 13 , 16 or 16a . The method is as follows.

[0072]

Embedded image _{a) Y sub} is des aminopyrazole compound of Formula 18 is hydrogen, wherein Y is amino (Ia), i.e. formula 7,
8, 13, 16 or 16a and nitrous acid aminopyrazole compounds by organic alkyl nitrite or required, such as nitrite t- butyl, about -20 ° C. ~ about 180 ° C. in an inert organic solvent such as tetrahydrofuran , Preferably from about 10 ° C to about 100 ° C.

B) Compounds of formula 18 wherein Y _sub is halogen, cyano or alkylsulfenyl are of the formula (I
a), i.e. the compound of formula 7 , 8 , 13 , 16 or 16a is deaminated as described in method Va above and then immediately converted to bromoform, cupric chloride, cupric cyanide or dimethyl disulfide By quenching with a material such as The reaction is generally carried out in an inert organic solvent such as anhydrous acetonitrile, typically from about -20C to about 180C, preferably from about 10C to about 100C.
Performed at a temperature of ° C. Other compounds where Y _sub is alkylsulfinyl or alkylsulfonyl (ie, alkylsulfoxide (n = 1) or alkylsulfone (n = 2, respectively)) were prepared as described for the conversion of 7 to 8 in Method Ia. It is produced by the oxidation reaction that takes place.

Method VI Y _sub is alkoxy and X, Z, R ₂ , R ₃ , R
₄ and a compound of formula _{R 5} is as defined in the general formula (I) (I), further compounds of formula 18 or (Ic), wherein _{Y sub,} which is prepared in a manner Vb is halogen 18 It is manufactured from the compound of. This process will be described below.

[0075]

Embedded image a) An intermediate hydroxy compound of formula 19 converts a compound of formula 18 wherein Y _sub is a halogen to the corresponding Grignard reagent or the corresponding lithium derivative according to known methods. J. J. Lewis et al. Or
g. Chem. , Oxodiperoxymolybdenum (pyridine) (hexamethylphosphoric triamide) by a method similar to that described in, 42 , 1479 (1977).
It is manufactured by processing using (MoOPH). Alternatively, the aforementioned Grignard reagent or lithium derivative is reacted with a trialkyl borate,
F. Hawthorne, J.M. Org. Chem. , 2
2 , 1001 (1957) or R.E. W. Hoffma
nn and K.I. Ditrich, Synthesis (1
983), 107, and oxidized with hydrogen peroxide or another oxidizing agent to produce the hydroxy analog.

B) Compounds of formula 18 or (Ic) wherein _Ysub is alkoxy can be prepared by various standard alkylation methods, such as alkyl halides or sulfates in an inert solvent from about -20 ° C to about 200 ° C. It is prepared from an intermediate hydroxy compound of formula 19 by using at a temperature of ° C.

Method VII X wherein S (O) _n R ₁ (where n and R ₁ are as defined above) is alkylsulfenyl, haloalkylsulfenyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl Wherein Y, Z, R ₂ , R ₃ , R ₄ and R ₅ have the meaning of the definition of general formula (I),
Compounds of formula (Id) as further defined below, in particular compounds of formula 24
Or 24a or 26 or 26a ,
Starting from an intermediate compound of formula (V), where Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined in general formula (I), X is chlorosulfonyl by the following method: Certain intermediate 21 or intermediate 2 wherein X is thiocyano
5 is obtained. Any of these intermediates are converted to the corresponding disulfide intermediate 22 , which is then converted to a sulfphenyl compound 24 or 26 where X is SR ₁ where R ₁ is as defined. And can be further oxidized to the corresponding sulfoxide or sulfone compound 24a or 26a where X is S (O) _n R _1, where n is 1 or 2. This process is as follows.

A) X is chlorosulfonyl, Y,
Intermediates of formula 21 wherein Z, R ₂ , R ₃ , R ₄ and R ₅ have the meaning defined in formula (I) can be prepared according to methods Ib, IIIa-
IIIb, IVa-IVd, Va-Vb and VIa-V
Prepared from an intermediate of formula (V) prepared from a compound of formula 4 by combining methods of introducing Y and Z substituents according to Ib, by treating it with chlorosulfonic acid or dichlorosulfonic acid. The reaction is carried out in the presence of an organic solvent such as methylene chloride, chloroform, carbon tetrachloride or dimethylformamide or using chlorosulfonic acid as a solvent at a reaction temperature of about -10C to about 160C. Representative methods for chlorosulfonation of aromatic compounds are described in March, “Advanced
d Organic Chemistry ", McGr
aw-Hill publ. (1968), p. 402
Has been reported to.

[0079]

Embedded image b) X is a disulfide moiety, Y, Z, R ₂ ,
The definitions of R ₃ , R ₄ and R ₅ are as given for the definition of formula (I). The intermediate disulfide compound of formula 22 is prepared using a reducing agent such as triphenylphosphine.
It is prepared from a compound of formula 21 by treatment at a reaction temperature of about -10C to about 120C in the presence of an organic solvent such as tetrahydrofuran, dichloromethane or toluene. Representative examples of how to be reduced to p- tolyl disulfide, J. Org. Chem. , 45 , 4792 (19
80). Alternatively, disulfenylation is
It is carried out using a metal carbonyl such as hexacarbonylmolybdenum in anhydrous tetramethylurea. The process of this reaction is described in Alper, Angew. Chem. I
net nat. Edit, 8 , 677 (1969). The reaction of the present invention is as follows.

[0080]

Embedded imagec) Y, Z, R₂, R₃, R₄And R₅Is defined by the expression
Given for the definition of (I), wherein X is halo
Alkylsulfenyl, preferably perhaloalkyls
Luphenyl R₆S [where R₆Is CFR₇R₈(R₇Passing
And R₈Is an F, Cl, Br or perfluoroalkyl group
Is a compound of formula (I)24
The compound of the formula is22And a compound of the formula23Perhalal of the
Can compound Halo-CFR₇R₈[Halo here
Cl, Br or I, R₇Is F, Cl or Br
And R₈Is F, Cl, Br or perfluoroal
A free radical R₆, CFR₇R₈(Compound
object23Halo-CFR₇R₈Of origin)
Produced by reaction with a reducing agent
It is. If the reducing agent is zinc, aluminum, cadmium
Or compounds containing manganese metal or sulfur oxides
Such as dithionite or hydroxymethyls
Preferably, it is selected from luffinate. alkalinity
Dithionite, alkaline earth or metal dithionite
The salt has the formula M_m(S₂O₄Where m is the valence of the metal M
Therefore, it may be 1 or 2.] Subthion
Use acid salts or hydroxymethylsulfinates
In some cases, a base is required. The base is, for example, alkali gold
Genus hydroxide, alkaline earth metal hydroxide, ammonia,
Alkylamine, triethylbenzylammonium,
Or disodium phosphate, sodium metabisulfite, sulfite
Weak like sodium hydrogen oxyhydrate or sodium borate
It is a salt of an acid. The solvent used for the reaction is dithionite
Or hydroxymethylsulfinate and compounds2
2as well as23Can be dissolved. Effective solvents are
Cetonitrile, dimethylformamide, formamide,
Dimethylacetamide, hexamethylphosphoramide,
N-methylpyrrolidone, dimethyl sulfoxide or
Ruholan. The reaction temperature is about 10 ° C to about 100 ° C.
You. A typical method is described in Maggiolo,J. A
m. Chem. Soc., (1951), 5815 and
P. W. Feit,Acta. Chem. Scan.,
16, 297 (1962).
It is like. The reaction of the present invention is represented by the following formula.

[0081]

Embedded image d) X is cyanothio and Y, Z, R ₂ , R ₃ , R ₄
And R ₅ is an intermediate compound having the meaning given in the definition of formula (I), ie the compound of formula 25 , is obtained by converting the compound of formula (V) from bromine and an alkali metal thiocyanate such as potassium thiocyanate. It is prepared by treating with a salt in a suitable solvent such as methanol at about -78 ° C to about room temperature. The solvent is inert to the reactants,
In addition, the reactants must be capable of solvolysis.

[0082]

Embedded image e) Alternatively, a compound of formula 24 wherein X is a haloalkylsulfenyl, preferably a perhaloalkylsulfenyl, sequentially oxidizes the compound of formula 25 to form an intermediate disulfide compound of formula 22 which is then converted to the corresponding compound of formula 24 To a haloalkylsulfenyl. Oxidation involves reducing a reducing agent such as hydrogen peroxide with an alkali metal hydroxide such as sodium hydroxide or an amine such as ammonia in a suitable solvent such as alcohol, water, tetrahydrofuran, halogenated alkanes or mixtures thereof. The reaction is carried out in the presence at a reaction temperature of about -70 ° C to about 55 ° C. A typical method is described in
Maggiolo, J .; Am. Chem. Soc. ,
(1951), 5815 and P.M. W. Feit, Act
a. Chem. Scan. , 16 , 297 (1962)
Reported in The haloalkylsulfenyl compounds of formula 24 are prepared by reacting a disulfide intermediate compound of formula 22 with a suitable perhaloalkane, optionally in the presence of a reducing agent such as a metal consisting of zinc, aluminum, cadmium or manganese. You.

[0083]

Embedded image f) Another compound of formula (I) wherein X is alkylsulfenyl or haloalkylsulfenyl and Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined by formula (I), That is, the compound of formula 26 is obtained by converting the compound of formula 25 using a suitable alkyl halide R ₁ Halo, where R ₁ is alkyl or haloalkyl as defined above, preferably alkyl iodide or alkyl bromide. In a suitable solvent such as an alcohol, preferably the corresponding alkyl alcohol, in the presence of a basic catalyst such as an alkali metal hydroxide or alkali metal carbonate, about -2.
It is produced by processing at a reaction temperature of 0 ° C to about 75 ° C.

[0084]

Embedded image g) X is alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl [X = S (O) _n R ₁ (where n is 1 or 2)], and Y, Z, R ₂ , R ₃ , compounds of formula (I) having the formula 24a also <br/> is 26a R ₄ and _{R 5} are as defined in formula (I) 24 or 2
The compound of No. 6 is produced, for example, by the oxidation method described in Method Ia.

Generalization of the Methods The methods or processes of the above synthesis are not limiting and therefore the compounds of the present invention and intermediates and starting materials (especially pyridine) will be apparent to those skilled in the art and are generally known and used. Or by application or adaptation of synthetic methods described in the chemical literature. In this regard, it will be appreciated that, for example, the order of the synthetic chemistry steps can be performed in any suitable order, appropriate protecting groups can be used, and substituents can be incorporated at convenient times. I want to.

In general / overall, the synthesis method described above comprises:
It can be represented by the method of the invention described below.

P ₁ . Process for the preparation of a compound of formula (I) having formula (Ia):

[0088]

Embedded image Wherein R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I), and X is alkylsulfenyl, haloalkylsulfenyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl,
Haloalkylsulfonyl, halogen or nitro, and Z is cyano or halogen].

A) Equation 4 :

[0090]

Embedded image Wherein R is C _1-4 lower alkyl and the amino is optionally protected as required. The intermediate ester compound is _first converted to a halogenated sulfenyl R ₁ SHA
lo (where R ₁ is alkyl or haloalkyl) in an organic reaction medium, optionally in the presence of an acid acceptor such as a tertiary amine, wherein X is alkylsulfenyl or haloalkylsulfenyl. Equation 5
To form an intermediate sulfenylated compound of formula 5 which is prepared in an inert solvent in the presence of a catalyst at about -78 ° C to about 5 ° C.
Amidation with ammonia at a temperature of 0 ° C. or, if necessary, hydrolysis of the intermediate ester 5 to the corresponding acid, conversion to the acid chloride and finally reaction with ammonia to give the intermediate of the formula 6 A carboxamide compound is obtained, which is then dehydrated, optionally in an organic solvent,
At a temperature of about 30 ° C. to about 18 ° C., Z is cyano and X
Is an alkylsulfenyl or haloalkylsulfenyl, ie a compound of formula 7 , and then optionally oxidizing compound 7 by known methods, such as peracids, so that X is S ( O) _n R ₁ [where n is 1 or 2 and R ₁ is as defined above]
Ie, X is an alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, to give another compound of formula (Ia), ie a compound of formula 8 .

[0091] b) an intermediate ester compound of formula 4, in a manner similar to that described for process P _{1 a,} to give the intermediate carboxamide compound of formula 9 according to the amidation process First, then Equation 10 is converted according to the dehydration process And then following the sulfenylation process to obtain R ₁ SH
alo to give a compound of formula (Ia), ie a compound of formula 7 , which is then optionally oxidized to give a compound of formula (I
The compound of a), ie the compound of formula 8 , is obtained.

C) The intermediate ester compound of formula 4 is first halogenated or nitrated according to a known method,
X is to give the intermediate ester compound of formula 11 is a halogen or nitro, which in a manner similar to that described for process P _{1 a,} first reacted according to the amidation process to obtain an intermediate carboxamide compound of formula 12 which is then Is converted to a compound of formula (Ia) wherein Z is cyano and X is halogen or nitro, ie a compound of formula 13 , following the dehydration process.

[0093] d) The intermediate ester compound of formula 4 is first converted to an intermediate sulfenyl ester compound of formula 5 according to the above process P _{1 a} or the process P
According _{1 c} into a halogenated or nitrated intermediate ester of formula 11, followed by hydrolysis according to known methods a compound of formula 5 or 11, an intermediate compound of formula 14 Z is carboxy, which is then formula 15 and then reacted with a halogen according to the Fundskie's method, wherein Z is a halogen,
A compound of formula (Ia) wherein X is alkylsulfenyl, haloalkylsulfenyl, halogen or nitro and Y is amino, ie a compound of formula 16 , is obtained, where X is alkylsulfenyl or haloalkylsulfenyl. the compound of formula 16 is oxidized according to the method described in process P _{1 a,} Z is halogen, X is alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl and Y is amino wherein A compound of formula (Ia), ie of formula 16a , is obtained.

P ₂ . Process for the preparation of a compound of formula (I) having formula (Ib):

[0095]

Embedded image Wherein X, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined in the general formula (I), and the amino derivative Y is an alkylamino, dialkylamino, trialkylammonium salt, cyano Alkylamino, alkoxyalkylamino, alkylcarbonylamino, haloalkylcarbonylamino, alkoxycarbonylamino,
Alkylaminocarbonylamino, dialkylaminocarbonylamino or alkoxyalkylideneimino].

[0096] a) process _{P 1 a~P} 1 d formula is prepared according to the method described in (Ia):

[0097]

Embedded image Wherein X, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined above, by converting an unsubstituted (or cyano or alkoxy substituted) alkyl such as alkyl iodide or dialkyl sulfate. Agent and an inert solvent at about 0 ° C.
Reaction at a temperature of about 160 ° C., optionally in the presence of a base or optionally by known Eschweiler-Clark reductive methylation using formaldehyde and formic acid, the amino derivative Y is alkylamino, dialkylamino, A compound of formula (Ib) is obtained which is a trialkylammonium salt, cyanoalkylamino or alkoxyalkylamino.

B) reacting the compound of formula (Ia) with an alkylcarbonyl halide or haloalkylcarbonyl halide in an organic solvent at a temperature of about -10 ° C to 100 ° C, optionally in the presence of an acid acceptor Let me
A compound of formula (Ib) is obtained in which the amino derivative Y is an alkylcarbonylamino or a haloalkylcarbonylamino.

C) The compound of formula (Ia) is first reacted with phosgene to give an intermediate chlorocarbonylamino or isocyanate compound which is then reacted with an alkyl alcohol, alkylamine or dialkylamine in an organic solvent in about- Reaction at a temperature of from 20 ° C. to about 100 ° C., optionally in the presence of a base, gives a compound of formula (Ib) in which the amino derivative Y is alkoxycarbonylamino, alkylaminocarbonylamino or dialkylaminocarbonylamino.

D) reacting the compound of formula (Ia) with an alkyl orthoformate in the presence of a catalyst at about -20 ° C to about 180 ° C;
And optionally in an organic solvent, to give a compound of formula (Ib) in which the amino derivative Y is an alkoxyalkylideneimino, in particular an alkoxymethylideneimino.

P ₃ . Process for preparing a compound of formula (I) having formula (Ic):

[0102]

Embedded image Wherein X, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined in the general formula (I), and Y _sub is hydrogen, halogen, cyano, alkylsulfenyl, alkylsulfinyl, Alkylsulfonyl or alkoxy].

[0103] a) process _{P 1 a~P} 1 d produced by the method according to Formula (Ia):

[0104]

Embedded image Wherein X, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined above, by reacting the alkyl nitrile or optionally nitric acid with an inert organic solvent at about −20 ° C. Deamination by known methods, such as at a temperature of about 180 ° C., converts the compound of formula (Ia) wherein Y is amino to its corresponding diazonium salt, which is then converted to a corresponding diazonium salt according to known methods using a quenching agent. By quenching the diazonium salt at a temperature between -20 ° C and about 180 ° C, Y
_sub is hydrogen, halogen, to give the compound of the cyano or alkylsulfenyl formula (Ic), followed by necessary oxidized according to the method of process _{P 1} a compound _{Y sub} is _{alkylsulfenyl,} is _{Y sub} Compounds of formula (Ic) which are alkylsulfinyl or sulfylsulfonyl are obtained.

[0105] b) the the compound of formula (Ia), are first reacted by such substitution deamination according to process P _{3 a,} Y _sub is to give the compound of formula (Ic) is halogen, then the compound Converting to an organomagnesium or organolithium derivative, reacting the organometallic derivative with an oxidizing agent such as oxodiperoxymolybdenum (pyridine) (hexamethylphosphoric triamide) or trialkyl borate, and hydrogen peroxide, An intermediate hydroxy compound of formula 19 is obtained, which is finally reacted with an alkylating agent in a known solvent at a temperature of from about -20 ° C to about 200 ° C by a known alkylation method, wherein Y _sub is alkoxy. The compound of formula (Ic) is obtained.

P ₄ . Process for preparing a compound of formula (I) having formula (Id):

[0107]

Embedded image [Wherein, Y, Z, n, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Is as defined in general formula (I),
(O) _n R ₁ X is alkylsulfenyl, haloalkylsulfenyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl].

A) Processes P ₁ b, ab and P of P _2
3 of one or more processes in accordance Y and Z substituents are prepared from the intermediate compound of formula 4 of process P ₁ by a combination of methods for introducing expression to b (V):

[0109]

Embedded image Wherein Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined above, and Y and Z are optionally protected as required. Reaction with a mixture of metal thiocyanates gives an intermediate compound of formula 25 where X is thiocyano, which is then treated with an alkylating agent, optionally in the presence of a base, to give X
Is a compound of formula 26 , i.e., is an alkylsulfenyl or a haloalkylsulfenyl, i.e., a compound of formula (Id), or, if necessary, the intermediate compound 25 wherein X is thiocyano is first oxidized to give the corresponding intermediate disulfide compound 22 , which is then reacted with a perhaloalkane, optionally in the presence of a reducing agent, to give a compound of formula 24 wherein X is a haloalkylsulfenyl, especially a perhaloalkylsulfenyl, ie a compound of formula (Id), Finally If necessary, X is compound 24 also <br/> is alkylsulfenyl or haloalkylsulfenyl is oxidized by known methods similar to 26 in process P _{1 a,} X is alkylsulfinyl, haloalkylsulfinyl, Is alkylsulfonyl or haloalkylsulfonyl Compounds of formula 24a or 2 6 a, i.e. obtain the compound of formula (Id).

[0110] b) an intermediate compound of formula (V), is first reacted with chlorosulfonic acid or dichloro acid, X is to give the intermediate compound of formula 21 is chlorosulfonyl, then triphenyl chlorosulfonyl compound 21 By reacting with a reducing agent such as phosphine, process P ₄
give the same disulfide intermediate 22 as described in a, finally transformed by the method described disulfide 22 to process P _{4 a,} X is haloalkylsulfenyl, particularly compounds of Formula 24 is a perhaloalkyl sulfenyl,
That is, a compound of formula 24a wherein X is haloalkylsulfinyl, especially perhaloalkylsulfinyl or haloalkylsulfonyl, especially perhaloalkylsulfonyl, i.e., obtaining a compound of formula (Id) or optionally oxidizing the sulfenyl compound 24 , The compound of (Id) is obtained.

The compound of the formula (I) thus produced can be converted to an acid addition salt by a known method.

P ₅ . Method for producing the ester compound of formula 4 :

[0113]

Embedded image Wherein R ₂ , R ₃ , R ₄ and R ₅ are as defined in general formula (I), and R is C _1-4 lower alkyl. Obtained by acid neutralization of the enolate salt Reacting the resulting C _1-4 alkyl 2-oxo-3-cyanopropionate compound of formula 2 with a 2-pyridylhydrazine compound of formula 3 substituted by R ₂ -R ₅ as defined above. , Of the formula 4

P ₆ . A method for preparing the carboxamide compound of Formula 9 :

[0115]

Embedded image Wherein R ₂ , R ₃ , R ₄ and R ₅ are as defined in general formula (I). Amidating the ester compound of formula 4 obtained by process P ₅ with ammonia Consisting of

P ₇ . A method for preparing the nitrile compound of Formula 10 :

[0117]

Embedded image Wherein R ₂ , R ₃ , R ₄ and R ₅ are as defined in general formula (I). The carboxamide compound of formula 9 obtained by process P ₆ is dehydrated using a dehydrating agent Consisting of

P ₈ . Method for the preparation of a compound of formula (I) wherein X, Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I): introducing X, Y and Z substituents formula according to any of the manufacturing method of the process _P 1 to P ₄ for
4 ).

P ₉ . Method for the preparation of a compound of formula (I), wherein X, Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I): according to any of processes P _{1 to} P ₈ Intermediate compounds 4 , 5 , 6 , 9 , 9 , 10 , 11 , 12 , 1
Reacting any one of 4 , 19 , 21 , 22 , 25 or (V).

Representative Compounds of the Invention The compounds in Table 1 show some of the preferred compounds within the above general formula (I) or (IIa) or (IIb), which are generally known And can be prepared by the synthetic methods or processes described herein, with the appropriate choice of reagents, conditions, and working procedures that will be apparent to those skilled in the art.

[0121]

[Table 1]

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[0125]

[Table 5]

[0126]

[Table 6]

[0127]

[Table 7]

[0128]

[Table 8]

[0129]

[Table 9]

[0130]

[Table 10]

[0131]

[Table 11] Examples 1-27 and 28-33 below further illustrate some of the more preferred compounds (I) and (II) of the present invention that have been prepared. Details of the intermediates and typical synthetic methods used to prepare the compounds of the present invention are specifically disclosed below for the compounds of Examples 1-7. Other compounds were prepared using similar synthetic methods or variations thereof as described in the procedures applicable to this given compound. Examples of these compounds are listed in Table 2 (where R ₂ is C1, R ₃ and R ₅ are H, and R ₁ , n, Y and R ₄ are as defined above) and 2A Table (where R ₂ is C1, R ₄ is CF ₃ , R ₃ and R ₅ are H, Z, X and Y
Is as defined above). The melting points of the reported compounds were determined on the compounds and also represent the average of the observed melting points or the average of several separate melting point measurements. further,
One or more spectroscopic analyzes (IR, NMR, GC / MS, etc.) were performed on each compound for identification and confirmation of chemical structure.

[0132]

【Example】

Example 1 1- [2- (3-chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-chlorodifluoromethyls
Preparation of l-phenyl-5-aminopyrazole Reaction formula 1-A a) Intermediate: 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -3-ethoxycarbonyl-5-
Preparation of aminopyrazole A large beaker was charged with 250 ml of water, 250 g of ice and the sodium salt of ethyl-2-oxy-3-cyano-2-propenoate (26.8 g, 164.8 mmol). The pH of the suspension was adjusted to 2 using dilute aqueous sulfuric acid. Sodium chloride (40 g) was added and the solution was
Extracted with OAc. The organic layer was dried over MgSO _4, filtered, and concentrated. Immediately add the crude acyl ester to EtOH
(175 ml) and 2-hydrazino 3-chloro-5-trifluoromethylpyridine (22.5 g, 10
6.3 mmol) was added to the round bottom flask. The reaction was heated at reflux for 2 hours, then sodium bicarbonate (9.
(8 g, 116 mmol) was added and reflux was continued for 2 hours.
At this point, the reaction mixture was cooled and 600 ml of ether
And filtered through a pad of Celite. The filtrate was washed with water, 10% aqueous hydrochloric acid and water. The organic layer was dried over MgSO _4, filtered, and concentrated. The resulting solid was recrystallized from EtOH and washed twice with petroleum ether to give the desired product as a dark brown solid (2
5.63 g, yield 72%). 157.5 ° C.

¹ H NMR (CDCl ₃ ) -δ 1.35
(T, 3H, J = 7 Hz), 4.38 (q, 2H, J =
7 Hz), 4.62 (brs, 2H), 6.12
(S, 1H), 8.19 (s, 1H) and 8.68
(S, 1H).

B) Intermediate: 1- [2- (3-chloro-5)
-Trifluoromethyl) pyridyl] -3-ethoxycarbonyl-4-chlorodifluoromethylsulfenyl)-
Round bottom flask with a manufacturing concentrator of 5-amino-pyrazole, _{N 2} under, acetic 30m
pyrazole in Example 1 (Example 1a) (10.0 g, 29.
9 mmol). Next, chlorodifluoromethylsulfenyl chloride (3.3 ml, 32.9 mmol) was added in one portion. The reaction was stirred overnight at room temperature. TLC analysis showed no starting material. Dilute the reaction with CH ₂ Cl ₂ (200 ml) and add water (2 × 1).
00 ml), aqueous sodium bicarbonate solution (2 × 50 ml)
And a saturated aqueous solution of NaCl. Dehydrate the organic layer (M
gSO ₄ ), filter and concentrate to give the desired product.
08 g (97%) were obtained. 142.5 ° C.

¹ H NMR (CDCl ₃ ) -δ 1.39
(T, 3H, J = 7 Hz), 4.42 (q, 2H, J =
7 Hz), 5.4 (br s, 2H), 8.2 (s, 1
H) and 8.72 (s, 1H).

C) Preparation of 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -3-cyano-4-chlorodifluoromethylsulfenyl-5-aminopyrazole Literature ( Tetrahedron Letters. 19)
79, 4907), a fresh solution of dimethylaluminum amide was prepared. Under a N ₂ atmosphere, pyrazole (Example 1b) (12.1 g, 26.8 mm) was added to 200 ml of CH ₂ Cl ₂ in a round bottom flask equipped with a concentrator.
ol) was dissolved. Dimethyl aluminum amide (45
ml, _CH 2 Cl ₂ in 1.2M) was added and the reaction was stirred for 1.5 hours at room temperature and heated at reflux overnight. The reaction was cooled and poured into a large beaker. Ice and water (300 ml) were carefully added. Next, a 10% aqueous hydrochloric acid solution was added until the aqueous layer became acidic. The layers were separated and the aqueous layer was separated from CHCl ₃ (2
00ml) and EtOAC (100ml).
Combine the organic layers and wash with water and saturated aqueous NaCl,
Dry over MgSO ₄ , filter and concentrate to give 10.79 g of a brown solid.

The brown solid was placed in a round bottom flask with 60 ml of POCl ₃ . The reaction was heated at reflux for 5 hours and stirred at room temperature overnight. Next, the POCl ₃ was removed under vacuum. 300 ml of water and 200 ml of EtOAC were added to the residue. The layers were separated and the aqueous layer was extracted with EtOAC. Combine the organic layers and wash with a saturated solution of NaHCO ₃ and MgSO ₄
Dehydrated above and concentrated to give 7.48 g of crude product. The aqueous layer was adjusted to pH 8 with 10% aqueous NaOH and extracted with EtOAC to give another crude product, 3.14 g.

Silica gel flash chromatography (eluent: 20% CH ₂ Cl ₂ / hexane to 75% CH ₂
Cl ₂ / hexane) yields 25% of the desired pure product
Was obtained in a yield of Melting point 122 [deg.] C.

¹ H NMR (CDCl ₃ ) -δ 5.76
(Br 4, 2H), 8.26 (s, 1H) and 8.7
3 (s, 1H).

Example 2 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-chlorodifluoromethyls
Round bottom flask equipped with a condenser of Rufiniru-5-aminopyrazole, _{N 2} under, 1- [2-
(3-chloro-5-trifluoromethyl) pyridyl]-
3-cyano-4-chlorodifluoromethylsulfenyl-5-aminopyrazole (0.5 g, 1.24 mmol
l), TFA (10 ml) and 30% H ₂ O ₂ (120
μl) was added thereto, and the reaction solution was stirred at room temperature for 6 days. next,
The reaction mixture was poured on ice (25 g) and extracted with EtOAC. The organic layer was washed with a 10% aqueous solution of Na ₂ S ₂ O ₃ (1 ×),
NaHCO ₃ aqueous solution (4 ×) and washed with water, MgSO ₄
Dried over, filtered and concentrated. The crude sulfoxide is purified by silica gel flash chromatography (eluent 75%
Purification with (CH ₂ Cl ₂ / hexane) provided the desired product (0.43 g, 83%) as a white crystalline solid. 155.5 ° C.

¹ H NMR (CDCl ₃ ) -δ 7.00
(Br s, 2H), 8.33 (s, 1H) and 8.7.
6 (s, 1H).

Example 3 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-chlorodifluoromethyls
Round bottom flask equipped with a condenser of Ruhoniru-5-aminopyrazole, _{N 2} under, CHCl ₃
1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -3-cyano-4-chlorodifluoromethylsulfenyl-5-aminopyrazole (0.5 g, 1.24 mmol) contained in 25 ml I put it. m-chloroperoxybenzoic acid (purity 80-85%, 0.75
g, 3 equivalents) was added to the reaction solution at once, and the mixture was heated under reflux overnight. The reaction was diluted with 50 ml of CHCl ₃ and 10% Na
Washed with aqueous OH (2 × 25 ml) and water (25 ml), dried over MgSO ₄ , filtered and concentrated. The crude sulfone _CH 2 Cl _2: hexane (1: 9) and recrystallized from a white solid 0.35 g (65%) was obtained.
154.5 ° C. ¹ H NMR (CDCl ₃ ) -δ
6.58 (br s, 2H), 8.32 (s, 1H) and 8.74 (s, 1H).

Example 4 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-chlorodifluoromethyls
Round bottom flask equipped with a condenser Le phenylpyrazole, under _{N 2,} aminopyrazole (Example 1c) (1.32g, 3.27mmo
l), t-butyl nitrile (1.9 ml, 16.3 mm
ol) and 60 ml of THF. The reaction mixture was stirred at room temperature for 4 hours. The solvent is removed in vacuo and the oily residue is flash chromatographed on silica gel (eluent 7).
(5% CH ₂ Cl ₂ / hexane) to give an oil of 1.0
2 g (80%) were obtained. The oil was crystallized from petroleum ether to give a pale yellow solid. 53 ° C.

¹ H NMR (CDCl ₃ ) -δ 8.26
(S, 1H), 8.63 (s, 1H) and 8.73
(S, 1H).

Example 5 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-dichlorofluoromethyls
Reaction Formula 1- Ba a) Intermediate: Preparation of 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -3-aminocarbonyl-5-aminopyrazole Concentrator round bottom flask equipped with, under _{N 2,} 1- [2-
(3-chloro-5-trifluoromethyl) pyridyl]-
3-ethoxycarbonyl-5-aminopyrazole (25
g, 74.7 mmol), 100 m of an aqueous NH ₄ OH solution
l, 300 ml of MeOH and 1 ml of water. The reaction was stirred at room temperature for 3 days. Next, ice was added to the reaction mixture and the aqueous solution was carefully adjusted to pH 1-2 with 10% HCl. The aqueous layer was washed with CH ₂ Cl ₂ (3 ×) and EtOAC
Extracted with (1 ×). Dehydrate the organic layer over MgSO ₄ ,
Filter and concentrate to 20.4 g (90%) of a brown solid
was gotten. This was used for the next reaction.

¹ H NMR (CDCl ₃ / DMSO-d
₆ )-δ 5.3 (br s, 2H), 6.02 (s, 1
H), 6.48 (brs, 1H), 6.75 (br
s, 1H), 8.13 (m, 1H) and 8.62 (m,
1H).

B) Intermediate: 1- [2- (3-chloro-5)
-Trifluoromethyl) pyridyl] -3-cyano-5-
Manufacturing addition funnel aminopyrazole, round bottom flask equipped with a thermometer and _{N 2} inlet, amide prepared in Example 5a (13.4 g, 43.
8 mmol). To this was added THF (75 ml) and pyridine (11 ml, 135.8 mmol) and the solution was cooled in an ice bath. While maintaining the temperature at −10 ° C.,
From the addition funnel, trifluoroacetic anhydride (13 ml, 91.
98 mmol) was added slowly. The solution was slowly warmed and stirred overnight. The reaction solution was CHCl ₃ (150 m
1), wash with water (2 × 50 ml), 10% HC
Washed with 1 aqueous solution (50 ml). The organic layer was dried over MgSO _4, filtered, and concentrated to a brown oil 17.03g was obtained. This is mixed with 300 ml of MeOH and NH ₄ OH
The mixture was placed in a flask together with 100 ml of the aqueous solution and refluxed for 8 hours. The solvent was evaporated, the residue was dissolved in EtOAC, washed with water and a saturated solution of NaCl, dried over MgSO ₄ and concentrated. The crude product was washed with cold _CH 2 Cl _2, when collected in a funnel, the solid 4.3g of white brown was obtained. The filtrate was concentrated and washed with cold CH ₂ Cl ₂ to give an additional 1.7 g (48% overall) of pure product.

¹ H NMR (CDCl ₃ / DMSO-d
₆ ) -δ 5.8 (br s, 2H), 5.9 (s, 1
H), 8.34 (m, 1H) and 8.73 (m, 1
H).

[0149] c) 1- [2- (3- chloro-5-trifluoromethyl) pyridyl] -3-reflux condenser cyano-4-dichlorofluoromethylthio sulfenyl-5-aminopyrazole and _{N 2} inlet In a round bottom flask equipped with the aminonitrile of Example 5b (3.58 g, 12.5 mm
ol) and 30 ml of acetic acid. Dichlorofluoromethylsulfenyl chloride (1.44 m
1, 13.7 mmol) and the reaction was heated at reflux for 2 hours and stirred at room temperature overnight. Methylene chloride was added and the organic layer was washed with water, a saturated aqueous solution of NHCO ₃ (2 ×) and water. The organic layer was dried over MgSO _4, filtered, and concentrated. The crude solid was purified by flash chromatography on silica gel (eluent 8: 1 hexane / EtOAC) to give 3.19 g (61%) of the desired product. Melting point 13
3 ° C.

¹ H NMR (CDCl ₃ ) -δ 5.76
(Br s, 2H), 8.22 (d, 1H, J = 2H)
z) and 8.66 (d, 1H, J = 2 Hz).

Example 6 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-dichlorofluoromethyls
Preparation of ruphenyl-5-ethoxymethylaminopyrazole
In a round bottom flask equipped with a thermometer and a simple distillation apparatus, the starting material aminopyrazole (Example 5c) (1.0 g, 2.
4 mmol) and 25 ml of triethyl orthoformate heated at the boiling point overnight. Triethyl orthoformate was removed under vacuum and the residue was dried in a vacuum open. NMR showed the desired ethoxymethylideneimino intermediate. The residue was washed with EtOH in a round bottom flask.
(20 ml) under N ₂ and cooled to 5 ° C. in an ice / salt bath. Sodium borohydride (24mg, 0.63mm
ol) and the reaction was stirred at 5 ° C. for 3 hours. NH ₄
The reaction was stopped by adding a saturated solution of Cl. The solvent was removed under vacuum to give a yellow oil. The oil was flash chromatographed on silica gel (eluent 7: 1 hexane /
Purification by EtOAC) provided 570 mg (55%) of the desired product as a pale white solid. Melting point 118.
5 ° C.

¹ H NMR (CDCl ₃ ) -δ 1.06
(T, 3H, J = 7 Hz), 3.38 (q, 2H, J =
7 Hz), 4.75 (d, 2H, J = 7 Hz), 6.7
(Brt, 1H, J = 7 Hz), 8.2 (d, 1H, J
= 2 Hz) and 8.7 (d, 1H, J = 2 Hz).

Example 7 1- [2- (3-Chloro-5-trifluoromethyl) pi
Lysyl] -3-cyano-4-trifluoromethylsulf
Preparation of phenyl-5-bromopyrazole 1- [2- (3-Chloro-5-trifluoromethyl) pyridyl] -3-cyano-4-trifluoromethylsulphenyl-5-aminopyrazole (1.0 g, 2. 58m
mol) in 25 ml of a bromoform solution was added t-butyl nitrite (1.5 ml, 12.9 mmol). The reaction was stirred overnight at room temperature. The bromoform was removed in vacuo and the oily residue was purified by silica gel flash chromatography: If (eluent 50% _CH 2 Cl ₂ / hexane) to afford the desired product 1.06 g (91%) was obtained. Melting point 54.5 ° C.

¹ H NMR (CDCl ₃ ) -δ 8.31
(M, 1H) and 8.90 (m, 1H).

Using a procedure similar to that of Example 1-7, Examples 8-27 in Table 2 and Example 28 in Table 2A were used.
-33 was obtained.

[0156]

[Table 12]

[0157]

[Table 13] Example 28 Acaricide, insecticide, aphid and nematicide
The following test procedure was carried out using the compound of Example 1-27 and the following test procedures were carried out for mites; certain insects, such as aphids, two caterpillars, flies, and two beetle larvae, Food habits,
And the activity and activity of the compounds of the present invention as insecticides against nematodes were measured. The specific species tested were: Test compounds (Examples 1-27) were formulated for use according to the following methods used for each test procedure.

For testing of mites, aphids, southern armyworms, ladybird beetles and tobacco moths, 160 mg of dimethylformamide, 838 mg of acetone,
ton X-172: 2 mg of a 3: 1 mixture of Triton X-152 (mainly anionic and nonionic low foam emulsifiers, which are anhydrous mixtures of alkylaryl polyether alcohols and organic sulfonates) and water.
A solution or suspension was prepared by adding 10 mg of the test compound to 99 g of the solution. As a result, a test compound concentration of 100 ppm was obtained.

For the housefly test, a formulation was first prepared in the same manner as above, but in 16.3 g of water, and the other components were adjusted to a concentration of 200 ppm with corresponding adjustments. Final dilution with an equal volume of a 20% by weight aqueous sucrose solution gave a test compound concentration of 100 ppm. If necessary, sonication was performed to completely disperse.

For testing of southern rice beetles, solutions or suspensions were prepared in the same manner as used for the first 200 ppm strength solution for housefly. Next, this 200p
Aliquots of the pm formulation were used and diluted with water depending on the required test concentration.

For the southern root knot nematode test and the southern armyworm, cotton aphid and aphid whole body test, dimethylformamide 250 mg, acetone 125
0 mg and 3 mg of the above emulsifier mixture were mixed with test compound 1
A stock solution or suspension was prepared by adding 5 mg. Next, water was added to make the total volume 45 ml, and the test compound concentration was 33 ppm. Sonicate as needed to completely disperse.

Green leafhopper and brown plant
For hopper testing, 10 mg of the test compound was added to a 50% aqueous acetone solution, and sonication was performed as necessary to prepare a 100 ppm stock solution or suspension. Dilute with 50% aqueous acetone as needed to obtain the required test concentration.

Test Procedure : Next, according to the following test procedure, the weight ppm (pa) of the test compound formulated above was measured.
Pesticide activity at specific concentrations, expressed as rts per million) was evaluated.

Dermatophagoid spider mite : The leaves of adult spider mites and larvae obtained from the stock culture were placed on the first leaves of two legumes growing in 6 cm beet pots. Within 24 hours, enough mites (150-200) for testing were transferred to new plants. Place the potted plant (one pot per compound) on a rotating turntable and air pressure 40 psi
g. 100 ppm test compound formulation 100 m using DeVilbiss spray gun set set to 100 m
l was sprayed enough to moisten and run off the plants. As an untreated control, 100 ml of a water-acetone-DMF-emulsifier solution without the test compound was also sprayed on the insect plants. Controls treated with either the commercial compound, Dicofol or Hexythiazox, formulated in the same manner, were also tested as standards. After leaving the sprayed plants for 6 days, the mortality of mobile organisms was measured.

Dermatophagoid spider mites (ovicidal test) : Eggs were obtained from adult Dermatophagoid spider mite in stock culture. The leaf with lots of insects from stock culture was placed on legumes without insects. About 2 females
After spawning for 4 hours, the leaves of the plant are crushed in a TEPP (tetraethyl diphosphate) solution to kill the organism,
It also prevented spawning. This soaking procedure was also performed after the plants had dried, but did not affect the viability of the eggs.
A potted plant (one pot per compound) was placed on a rotating turntable and air pressure 40 psig. De set to
100p using Vilbiss spray gun set
100 ml of the pm test compound formulation was sprayed on to give enough water to moisten and run off the plants. As an untreated control, 100 ml of a water-acetone-DMF-emulsifier solution without the test compound was also sprayed on the insect plants. A control treated with a commercially available compound, generally Demeton, formulated in the same manner was also tested as a standard. After leaving the sprayed plants for 7 days, the mortality of the eggs was measured and the remaining effects on hatched larvae were also recorded.

The buckthorn aphid : The adults and larvae of the buckthorn aphid were bred in potted small nasturtium plants. A potted plant with 100-150 aphids (one pot per compound) was placed on a rotating turntable and air pressure 40 psig. De set to
100p using Vilbiss spray gun set
100 ml of test compound formulation at pm were sprayed. As an untreated control, water-acetone without test compound
100 ml of the DMF-emulsifier solution was also sprayed on the wormed plants. A control treated with a commercial compound, malathion, formulated in the same manner was also tested as a standard. After spraying, the pots were left for one day, after which dead aphids were counted.

Southern armyworm : Potted legumes were placed on a rotating turntable and air pressure was 40 psig.
100 ml of the test compound formulation at 100 ppm was sprayed using a DeVilbiss spray gun set set at. As an untreated control, 100 ml of a water-acetone-DMF-emulsifier solution without the test compound was also sprayed on the insect plants. Controls treated with either the commercial compound, cypamethrin or sulprophos, formulated in the same manner, were also tested as standards. When the leaves were dry, the moistened filter paper was placed in a plastic cup with an inner surface.
Five randomly selected second instar southern armyworm larvae were placed in each cup, capped and left for 5 days. Larvae that could not move for the length of the body even when stimulated by poking were considered dead.

Tobacco moth: A potted cotton plant was placed on a rotating turntable and air pressure was 40 psig. 100 ml of the test compound formulation at 100 ppm was sprayed using a DeVilbiss spray gun set set at. As an untreated control, 100 ml of a water-acetone-DMF-emulsifier solution without the test compound was also sprayed on the insect plants. Controls treated with either the commercial compound, cypamethrin or sulprophos, formulated in the same manner, were also tested as standards. When the leaves were dry, they were placed in a plastic dish containing filter paper and moistened dental gauze.
One randomly selected second instar tobacco moth larva was placed in each cup, closed and left for 5 days. Larvae that could not move for the length of the body even when stimulated by poking were considered dead.

Green leafhopper and brown plant
Hopper : Potted rice plants were placed on a rotating turntable and sprayed with 60 ml of 0.5-10 ppm test compound using a turntable spray until run-down. As an untreated control, plants were also sprayed with an equal volume of 50:50 aqueous acetone without test compound. Controls treated with either the commercial compound, chloropyrifos or cypamethrin, formulated in the same manner, were also tested as standards. Once dried, add 2 of the above pots containing 20 randomly selected hoppers (primarily larvae).
Placed in greenhouse at 6 ° C. Next, the pots were covered with a ventilated incubator lid (wire gauge lid) and left for 4-5 days, after which the hopper mortality was examined.

[0170]Southern Awayothou systematic review on tomatoes
Value: This test, along with the assessment of southern root knot nematodes below
Carried out. Soil (first compound test screen) for nematode evaluation
In leaning, the soil concentration is 13.2 ppm, or
Tomato grown at a solution concentration of about 333 ppm)
Incorporation of compounds from roots and subsequent tomato leaves
Used for evaluation of systemic transport. Tomah at the end of the nematode test
Cut out the leaves and put them in a plastic container for Southern Awayo
A second instar larva of tow was attached. Larval mortality after about 5 days
Examined.

Southern armyworm (in sorghum and cotton), cotton aphid (in cotton) and cotton aphid (in sorghum)
Aphid-Histological evaluation : A stock solution of the compound was prepared and diluted appropriately as in the systematic / global test described above, and a fluid drug (solution concentration 150 ppm) was placed in a 6 cm pot planted with cotton and sorghum plants. ) Was distributed in a volume of 5 ml to give a soil concentration of 10 ppm. Cotton plants were pre-attached with cotton aphids about 2 days before treatment and aphids one day before treatment. After leaving the plants for about 4 days, cotton aphids and aphids were measured and mortality was calculated. Cotton and sorghum leaves were cut off, placed in separate plastic containers, and attached to the second instar larvae of southern armyworm. After about 5 days, the larval mortality was examined.

Ladybird Ladybird : A potted legume is placed on a rotating turntable and air pressure is 40 psi.
g. 100 ppm test compound formulation 100 m using DeVilbiss spray gun set set to 100 m
l was sprayed enough to moisten and run off the plants. As an untreated control, 100 ml of a water-acetone-DMF-emulsifier solution without the test compound was also sprayed on the insect plants. Controls treated with either the commercial compound, cypamethrin or sulprophos, formulated in the same manner, were also tested as standards. When the leaves were dry, the moistened filter paper was placed in a plastic cup with an inner surface. Five randomly selected second instar larvae of the ladybird were placed in each cup, closed and left for 5 days. Larvae that could not move for the length of the body even when stimulated by poking were considered dead.

Houseflies : Chemical Specials were prepared under the conditions adjusted for 4-6-day-old adult houseflies.
ties Manufacturing Associate
ation (Blue book, McNair-Do
land Co. , N .; Y. 1954; 243-24
4, page 261). The flies were anesthetized with carbon dioxide and immobilized, and the immobilized 25 male and female flies were transferred to a cage with a standard liquid food strainer and a wrapped surface. 10 ml of the 100 ppm test compound formulation was added to a souffle cup with an absorbent cotton pad. As an untreated control, 10 ml of a water-acetone-DMF-emulsifier-sucrose solution containing no test compound was similarly used. A commercial compound, malathion, formulated in the same manner was tested as a standard. The bait souffle cup was introduced into a food strainer before the anesthetized fly was put.
Twenty-four hours later, flies with no signs of movement upon stimulation were considered dead.

Southern cucumber beetle : 1.5 ml of an aqueous formulation consisting of a 200 ppm test compound formulation aliquot diluted with water in a jar containing 60 g of sandy loam soil with water so that the final soil concentration of the test compound is appropriate; 2ml
And 5 pre-germinated corn seeds. The jar was shaken well to evenly distribute the test formulation. After this, 20 southern rice beetle eggs were placed in the hole made in the soil. Next, vermiculite (1 ml) and water (1.7 ml) were added to the holes. Similarly, an untreated control was made using an equal aliquot of a water-acetone-DMF-emulsifier solution containing no test compound. In addition, treatment controls with commercial compounds formulated in the same manner (generally selected from terbufos, phonofos, folate, chlorpyrifos, carbofuran, isazofos and etprop) were used as standard compounds as needed. After 7 days, live turtle beetle larvae were counted using the well-known "Berleise" funnel extraction method.

Southern root knot nematodes : The infected roots of tomato plants containing egg masses of southern root knot nematodes are removed from the stock culture,
Then, it was shaken and washed with tap water to remove soil. The nematode eggs were separated from the root tissue and washed with water. A sample of the egg suspension was placed on a fine screen on a receiving bowl. The amount of water in the ball was adjusted to touch the screen. From the ball, the nymphs were collected on a fine screen. On the other hand, the bottom of a conical container is filled with coarse vermiculite, and then about 200 ml of sterilized soil is applied 1.5 times from the top.
cm. Next, an aliquot of the test compound formulation at 333 ppm was pipetted into a hole made in the middle of the soil in the conical container. A control treated with the commercial compound Fenamifos formulated in a similar manner was tested as a standard. As an untreated control, an aliquot of a water-acetone-DMF-emulsifier solution containing no test compound was used as well. Immediately after treating the soil with the test compound,
To the top of each conical vessel was added a young root-knot nematode at the 1000 second stage. Three days later, one healthy tomato seedling was transplanted into a conical container. A conical container containing the bred soil and tomato seedlings was placed in the greenhouse for three weeks. At the end of the test, the roots of the tomato seedlings were removed from the conical vessels and evaluated for galling on an evaluation scale as compared to the untreated control as follows: 1-Severe brush equivalent to the untreated control 3- Light Bulbs 4-Very Light Bulbs 5-No Bubbles No Suppression, That is, Inhibitions Immediately These results were then converted to ED ₃ or ED ₅ values (effective doses that scored a 3 or 5 floc).

Results of Use : The results of acaricidal, insecticidal and nematicidal activities for some of the representative compounds of Examples 1-27 of the present invention are described below. Alternatively, some of the compound examples were replaced with the indicated test species (BA, SAW, MB
B, HF, TSM, SCRW (abbreviation of common name) and the indicated doses are shown in Table 3. The results in Table 3 represent compounds that yield 70-100% mortality for the indicated test species as X. The compounds also inhibit tobacco moth, for example the compounds of Examples 1, 5, 6, 8 and 9 give 70-100% mortality at 100 ppm bait.

Some of the compounds further inhibit the development and growth of any insect larvae by taking in from the root at the soil concentration indicated in the above protocol. The results are as follows: 30-100% inhibition of southern armyworm on tomato (compounds of Examples 2, 3, 9, 10, 14, 18, and 22): 30-100% inhibition of southern armyworm on sorghum (Compounds of Examples 2, 9, 21 and 32): 30-69% inhibition of southern armyworm in cotton (compound of Example 2): 30-100% inhibition of cotton aphid in cotton (Examples 1, 9) , 14 and 21): and 30-100% inhibition of aphids in sorghum (Examples 9, 1)
0, 14, 21, 30, 31, 32 and 33).

Some of the compounds of the present invention control certain cereal pests, for example, at a test compound concentration of about 5-10 ppm in leaves, the compounds of Examples 2 and 10 reduce leafhoppers by about 90-100%. Examples 1, 2, 5, 10
And 18 are brown plant hops
er is suppressed by about 90-100%.

[0179] The compounds of the present invention also provides nematicidal activity, for example, the compound of Example 22, 23 and 26 ED ₃ to about 4-21kg / ha was obtained for SRKN.

In addition, the compounds of the present invention show reduced or anti-feeding properties against certain pests (eg leaf pests: southern armyworms and ladybugs).

The compounds of the present invention can be used against various pest species even at lower concentrations. For example: about 5 for leaf use
Can be used at 0-0.5 ppm or less; about 50-0.05 ppm or less for bait; used at about 1.0-0.01 ppm or less for soil it can.

In the above discussion and the results shown in Table 3, the compounds of the present invention were used at various concentrations. The use of 1 ppm (concentration of the compound in the used test solution in parts per million) of the solution, suspension or emulsion used for the foliage gives a spray dose of about 1000 l / ha (sufficient to run off) In view of the use of this, this corresponds to the use of about 1 g / ha of the active ingredient. Thus, about 6.25-500 ppm of leaf spray would correspond to about 6-500 g / ha. When used on soil, the depth of the soil is about 7.5 cm
Then, a soil concentration of 1 ppm corresponds to using about 1000 g / ha for the whole field. In other words, if the above 1 ppm soil concentration is used in a width of about 18 cm, about 1 cm
This corresponds to the use of 66 g / ha.

[0183]

[Table 14]

[0184]

[Table 15] Methods and Compositions As evident from the use as insecticides above, the present invention relates to compounds which are active as insecticides and include a number of arthropods, especially insects or mites; plant nematodes; or parasites or protozoa. The use of said compounds for the control of pests of the type is provided. Thus, the compounds of the invention are advantageously used, for example, in agricultural or horticultural crops, forest management, veterinary medicine or livestock breeding, or in public health practice.

Accordingly, a feature of the present invention is that an effective amount of a compound of the general formula (I) and more preferably a compound of the formula (II) (wherein the substituents are as defined above) is used (for example,
Pest control in an area comprising treating (using or administering) the area. Areas include, for example, pests themselves or places where they live or feed (plants, animals, humans, fields, buildings, houses, forests, orchards, waterways, soil, plants or animal products, etc.).

The compounds of the present invention are preferably used to control soil insects, such as corn leafworms, termites (especially for building protection), rootworms, scarab beetles, root weevil, stem borer, carab beetle, root aphid or maggot. Used for The compounds of the present invention can also be used to provide activity against pathogenic plant nematodes such as clubroot, cysts, daggers, lesions, or stem or bulb nematodes, or mites. For the control of soil pests, such as burs beetles, it is advantageous to use or incorporate an effective amount of the compound in the soil or seed or the root of a growing plant where the crop is or is to be planted.

Further, these compounds were used for leaves.
Alternatively, it may be useful for controlling some arthropods that eat above-ground parts of plants, especially some insects or mites via systemic action. It can also be used for plant roots or seeds and then be transferred systemically to the aerial part of the plant to control pests on leaves.

In the field of public health, the compounds of the present invention can be used to control a number of insects, especially filthy flies or other dipteran pests, for example, house flies, sand flies, water flies, horn flies, blood-sucking flies, bullflies, chironomids, nukaka, blackflies or Particularly useful for controlling mosquitoes.

The compounds of the invention can be used in the following applications and pests, including the following arthropods, especially insects or mites, nematodes, or parasites or protozoan pests: storage products, for example cereals containing cereal grains or flour , Peanuts, animal feed,
In the protection of wood or household products such as carpets and textiles, the compounds of the invention may be used in arthropods, especially beetles, moths or mites, including weevils, such as Ephesia sp.
p. (Flour moth), Anthrenus spp. (Himamarukatsuobushi), Tribolium sp
p. (Kokunustomodoki), Sitophilussp
p. (Grain weevil) or Acarus spp.
Useful for (tick) attacks.

Control of cockroaches, ants or termites or similar arthropod pests on household or industrial buildings with insects, or mosquitoes in waterways, wells, reservoirs or other running or pooled water Larvae extermination.

Termites such as Reticuliterm
es spp. , Heterotermes sp
p. The treatment of the foundation, building or soil to prevent attacks on the building by Coptermes spp.

In agriculture, butterfly moths Lepidoptera (Butterflies and moths)
For example, Heliothis spp. For example, Helio
this virescens, Heli
othis armigera and Heliothis
Zea, Spodoptera spp. For example,
exempta, S.M. frugiperda, S.M. ex
iqa, S.M. litoralis (Egyptian cotton helminth), eridania (southern armyworm) and M
amester configurata (Berth
a army worm); Earia spp. For example, E. insulana (Egyptophila tobacco), Pectinophora spp. For example, Pe
ctinophora gossypiella (pink tobacco moth), Ostrinia spp. For example, O. nubilalis (Europea americana), Trichoplusia ni (Cabbage beetle), Artogea spp. (Helminth of cabbage), Laphygmaspp. (Alexander), Agrotis and Amathes spp.
(Weevil), Wiseana spp. (Pori
na moth), Chilo spp (rice stalk borer), Tryporiza spp. And Diatr
aea spp. (Sugar cane borer and rice borer), Sparganothis prillian
a (Graph Berry Moth), Cydi
a pomonella, Archi
ps spp (fruit tree Hamakiga), Plutella
nylostella (Alga), Bupalus
pinarius, Cheimatobia bru
meta, Lithocolletis blanka
rdella, Hyponomeuta padell
a, Plutella maculipennis, M
alacosoma neustria, Euproc
tis chrysorrhoea, Lymantri
a spp. , Bucculix thurbe
riella, Phyllocnistis citr
ella, Euxoaspp. , Feltia bra
ssicae, Panolis flamemmea, Pr
odenia litura, Carpocapsa
pomonella, Pyrausta nubila
lis, Ephesia kuehniella, G
alleria melonella, Tineol
a bisselliella, Tinea pell
ionella, Hofmannophila pse
udospretella, Cacoecia pod
ane, Capus reticulana, Chor
istoneura fumiferana, Clys
ia ambiguellis, Homonamag
against adults, larvae and eggs of Nanime and Tortix viridana.

Coleoptera (Coleoptera), such as Hypotene
mus hampei (Hole)
esinus spp. Bark beetle, Anthon
omus spp. For example, grandis (Watami weevil), Acalimma spp. (Urchin beetle), Lema spp. , Psylliodes s
pp. , Leptinotarsa decemlin
eata (Colorado potato beetle), Diabrotica
spp. (Corn beetle), Gonoce
phalum spp. (Fake scarab beetle), Agri
otes spp. , Limonius spp. (Heteroptera), Dermolepidaspp. , Po
pilia spp. , Heteronychus
spp. (Peder beetle), Phaedon cochl
eariae (rapeseed beetle), Epitrix sp
p. (Flea beetle), Lissorhoptrus o
ryzophilus (rice water wee
vil), Meligethes spp. (Pollen beetle), Cetorhychus spp. , Rhyn
chophorus and Cosmopolites s
pp. (Root weevil), Anobium punct
atum, Rhizoperthadominica,
Bruchiius obectus, Acant
hoselides obectus, Hylot
rupes bajulus, Agelastica,
Psylliodes chrysocephala,
Epilachna varivestis, Atom
aria spp. , Oryzaephilus su
rinamensis, Sitophilussp
p. , Otorrhynchus sulcatu
s, Cosmoplites sordidus, Ce
uthorhynchus assimilis, H
ypera postica, Dermestes s
pp. , Trogoderma spp. , Anthr
enus spp. Attagenus spp. , L
yctus spp. , Malligethes aen
eus, Ptinus spp. , Nrptus ho
loleucrus, Gibium psylloi
des, Tribolium spp. , Tenebr
iomolitor, Conoderus spp. ,
Mellontha melonlontha, Amp
himalon solstitialis and Co
Against adults and larvae of steytra zealandica.

Heteroptera (Hemiptera and Homoptera) such as P
sylla spp. , Bemisia app. , T
liaureurodes spp. , Aphissp
p. , Myzus spp. , Negoura vic
iae, Phylloxera spp. , Adelg
es spp. , Phorodon humuli (hop damathon aphids), Aeneolamia
spp. , Nephotettix spp. (Ric
e leaf hoppers), Empoasca
spp. , Nilaparvata spp. , Per
Kinsiella spp. , Pyrrilla sp
p. , Aonidiella spp. (Red scale), Coccus spp. , Pseucoccu
s spp. , Helopeltis spp. (M
osquito bugs), Lygus spp. ,
Dysdercus spp. , Oxycarenus
spp. Nezara spp. , Eurygast
er spp. , Piesma quadrata, C
imex Lectularius, Rhodnius
prolixus and Triatoma sp
p. , Aspidiotus hederae, Aeu
rodes brassicae, Brevicor
yne brassicae, Cryptomyzus
ribis, Doralis, fabae, Dora
lis pomi, Eriosoma linger
um, Hyalopterus arundinis,
Macrosiphum avenae, Phorod
on humuli, Rhopalosiphum p
adi, Eucelis bilobatus, Ne
phototix cinctics, Leca
nium corni, Saissetia olea
e, Laodelphax striatellus
Against.

Hymenoptera, such as Athalia spp. And Cephus spp. (Habee), Atta sp
p. (Hakiriari), Diprion spp. , Ho
polcampa spp. , Lasius sp
p. Monomolium spp. , Poliste
s spp. , Vespa spp. , Vespula
spp. And Solenopsis spp.

For the order Diptera eg Delia spp. (Root worm), Atherigona spp. And Chlo
rops spp. , Sarcophaga sp
p. Musca spp. , Pharmia sp
p. Aedes spp. , Anopheles s
pp. , Simulium spp. (Stem fly), P
hytomyza spp. (Hanamogli), Cera
titis spp. (Flies), Culex sp
p. , Drosophila melanogaste
r. Ceratitis capitata, Dacu
s oleae, Tipula paradosa, C
alliphora erythrocephala,
Lucilia spp. , Chrysomyias
pp. , Cuterebra spp. , Gastro
philus spp. , Hypopobosca sp
p. , Stomoxys spp. , Oestrus
spp. , Hypoderma spp. , Taban
us spp. , Fannia spp. , Bibio
hortulanus. Oscinella fri
t, Phorbia spp. , Pegomyia h
For yoscyani.

For example, Thrips tabac
i, Hercinothrips femoralis
And Frankliniella spp. Against.

Orthoptera, such as Locusta and Schi
stockerca spp. (Locusts and crickets) For example, Gryllus spp. And Achetasp
p. For example, Blatta orientalis, Pe
riplanetamericana, Leucop
haea maderae, Blatella ger
mania, Acheta domesticus, G
ryllotalpa spp. , Locustam
igratria migratrioides,
Melanoplus differentialialis
And Schistocerca grearia.

Orders of the Order Collembola, for example Sminthurus
spp. And Onychiurusspp. (Collembola); Periplaneta spp. And Blat
tela spp. (Roach).

Isoptera, for example, Odontotermes
spp. , Reticuletermes spp. ,
Copttermes spp. (Termites).

Lepidoptera, such as Forticula sp
(Scissors).

Agriculturally important arthropods such as Akari
(Tick) For example, Tetranychus spp. , P
anonychus spp. , Bryobia sp
p. (Spider mite), Ornithonyssus sp
p. (Fowl mites), Eriophyes
spp. (Fushi mite) and Polyphadotar
Sonemus spp. Against.

For example, Lepisma sacch
against aria.

[0205] Lice orders, for example, Phylloxera v
astatorix, Pemphigus spp. , P
ediculus humanuscorporis,
Haematopinus spp. And Linsign
athus spp. Against.

Coat eyes, for example, Trichodicts
spp. And Damalineaspp. Against.

Siphonoptera such as Xeno
psylla cheopis and Ceratophy
lulus spp. Against.

Other arthropods such as Blaniulus
spp. Millipede, Scutigella sp
p. (Connecting class), Oniscus spp. (Wood
lice) and Triops spp. (Crustacea).

Isopodes, such as Oniseus asell
us, Armadillidium vulgare and Porcellio scaber.

Lippods such as Geophilus car
For pophagus and Scutigera spex.

Against nematodes that attack plants and trees important to agriculture, forestry or horticulture directly or by the transmission of bacterial, viral, mycoplasma or fungal diseases of the plants. For example, root-knot nematodes such as Meloidogyne sp.
p. (Eg, M. incognita): a cystic nematode such as Clobodera spp. (Eg G. rost
ochiensis); Heterodera sp.
p. (Eg, H. avenae);
s spp. (Eg, R. similis); diseased nematodes, such as Pratylenchus spp. (E.g. P. platensis); Belonolaimus
spp. (Eg, B. gracilis);
nchurus spp. (For example, T. semipen
etrans); Rotylenchulus sp
p. (Eg, R. reniformis); Rotyl
enchus spp. (R. robustus); H
elicotylenchus spp. (For example, H.
multiclectus); Hemicclipop
hora spp. (Eg, H. gracilis);
Criconemoides spp. (For example, C.I.
similis); Trichodorus spp.
(Eg, T. primitivus);
rsicaaudatum), Longidorus s
pp. (Eg, L. elongatus); Hople
laymus spp. (For example, H. coronatu
s); Apelenchoides spp. (Eg, A. ritzema-bosi, A. bessey
i); nematodes of stems and bulbs such as Ditylen
chusspp. (Eg, D. dipsaci).

In the field of veterinary medicine and livestock breeding or maintaining public health, vertebrates, especially warm-blooded vertebrates such as humans or livestock such as cattle, sheep, goats, horses, pigs, poultry,
Arthropods that are parasitic in or on dogs or cats,
Parasites or protozoa such as ticks (eg Ixod
es spp. , Boophilus spp. For example, Boophilus microplus, Ambly
Omma spp. Hyalomma spp. , R
hipicephalus spp. For example, Rhipi
cephalus appendiculatus, H
aemaphysalis spp. , Dermac
notor spp. , Ornithodorus sp
p. (For example, Ornithodorus mouba
ta) and mites (eg, Damalinia sp.)
p. , Dermahyssusgallinae, Sa
rcoptes spp. For example Sarcopes
scabiei, Psoroptes spp. , Ch
orioptes spp. Demodex sp;
p. , Eutrombicular spp. A)
carina; diptera (eg, Aedes sp.
p. , Anophelesspp. , Musca sp
p. , Hypoderma spp. , Gastero
philus spp. , Simulium sp
p. ); Hemi-wings (eg, Triatoma spp);
Phthirapter (for example, Damalinia
spp. Linogenathus spp. );
Siphonaptera (eg Ctenocep
halides spp. ); Dictopter
a (eg, Periplaneta spp, .Bl
atella spp. ); Hymenoptera
(E.g., Monomorium pharaonis)
For example; parasitic nematodes such as Trichostr
ongylidae, Nipponstrongylus
brasiliensis, Trichinella
spiralis, Haemonchus cont
ortus, Trichostrongylus co
lubriformis, Nematodirus b
atus, Ostertagis circumcin
cta, Trichostrongylus axis
i, Cooperia spp. And Hymenole
against gastrointestinal tract infections by the type of P. nana; , For example E
imeria tenella, Eimeria ac
ervulina, Eimeria brunett
i, Eimeria maxima and Eimeria
necatrix, Trypanosoms cruz
i, Leishamine spp. , Plasmo
dium spp. Babesis spp. , Tr
ichomonadidae spp. , Histom
ana spp. Giardia spp. , To
xoplasma spp. , Entamoeba h
istolytica and Theileria sp
p. For the control and treatment of protozoal diseases.

The present invention provides a method for controlling pests by using or administering to a zone an effective amount of a compound of formula (I) or (II) comprising treating the zone as described above.

In practical use for combating arthropods, especially insects or mites, or nematodes of plant pests, for example, the method involves using an effective amount of a compound of the present invention in the plant or medium in which the plant is grown. Consists of Such methods generally employ the active compound in the area to be combated with arthropods or nematodes at an effective rate ranging from about 0.005 kg to about 15 kg of active compound per hectare of treated area. Under ideal conditions, smaller amounts can be adequately protected, depending on the pest to be controlled. On the other hand, bad weather conditions, pest resistance and other factors may require the use of larger amounts of the active ingredient. The optimum ratio usually depends on many factors, such as the type of pest to be controlled, the type and growth stage of the plant with the insects, the spacing of the ridges and the use. Preferably, the effective rate of active ingredient is from about 0.01 kg / ha to about 2 kg / ha.

If the pest is soil-based, the active compound in the formulation will generally be distributed evenly in any convenient manner to the area to be treated (ie, for example, full surface treatment or banding). If desired, it can be used in the entire field or crop growing area, or near the seeds or plants to be protected from attack. The active ingredient can be poured into the soil by spraying the entire area with water, or may rely on the natural action of rainfall. During or after use, the optionally formulated compound can also be dispensed mechanically, for example by use of a plow, disk or drag chain. As long as it is germinated or after germination, it may be used before, during, or after planting. Furthermore, the extermination method includes treating the seeds before planting and obtaining an inhibitory effect after planting the seeds.

The method of controlling pests also comprises using or administering to the leaves of plants to control arthropods, especially insects or mites, that attack the aerial parts of plants or in the rays. Furthermore, the pest control method of the present invention also controls pests that eat away from the site of drug use of the plant, for example, phytophagous insects such as phytophagous insects. Get rid of by action. The compounds of the present invention can also reduce attack on plants by their antifeeding or insect repellent effects.

The compounds of the present invention and methods of controlling pests with the compounds of the present invention include crops for fields, feed, plantations, greenhouses, orchards or vineyards, houseplants, plantations or forest trees, for example:
Cereals (eg, corn, wheat, rice or sorghum), cotton, tobacco, vegetables (eg, beans, rape, cu)
rcurbits, lettuce, onions, tomatoes or peppers), field crops (eg potatoes, sugar beets,
Peanuts, soy or oilseed rape, sugarcane, pasture or forage crops (eg, corn,
Sorghum or lusern), plantations (eg, tea, coffee, bananas, coconut oil, coconut, gum or spices), orchards or small orchards (eg, drupes or pit fruits, citrus, kiwi, avocado, mango, olives or It is particularly useful for protecting walnuts, vineyards, houseplants, indoor or garden or park flowers or vegetables or shrubs, or forests, plantations or nursery trees (both deciduous and evergreen).

The compounds and methods of the present invention can be used, for example, to control wood (e.g., standing trees,
It is also useful for protecting felled, processed, preserved or architectural trees.

The compounds of the present invention or methods of use thereof may be used to store stored products, such as cereals, fruits, nuts, spices or tobacco, in their neat form or in a crushed or mixed form, from attack of moths, beetles, mites or weevils. Used to protect. Protects preserved animal products such as leather, wool, wool or feathers in their natural or processed form (for example as carpets or fabrics) from moth or beetle attack;
It also protects stored meat, fish or cereals from beetle, tick or fly attack.

Furthermore, the compounds of the present invention and methods of use thereof can be used to control, for example, control arthropods, parasites or protozoa which are harmful to humans and livestock or which transmit diseases or act as vectors for diseases. Typically (ticks, mites, lice, fleas, chironomids or sand flies,
It is also particularly useful for controlling noisy flies or fly larvae. The compounds of the present invention are particularly useful for combating arthropods, parasites or protozoa that are present in or in the skin of animal livestock or eat or suck on blood, for this purpose oral, parenteral Can be administered subcutaneously or topically.

Further, the compounds of the present invention can be used for coccidiosis, a disease caused by infection with a protozoan parasite of the genus Eimeria. The disease is an important potential cause of economic loss, particularly in livestock animals and birds reared or maintained in intensive conditions. For example, it also affects cattle, sheep, pigs or rabbits, but the disease is important in poultry, especially chickens. The administration of a small amount of the compound of the present invention, preferably together with food, has the effect of preventing or greatly reducing the development of coccidiosis. This compound is effective on both the cecal and small intestinal types. Furthermore, the compounds of the present invention can also show an inhibitory effect on oocytes by greatly reducing the number and sporulation of oocytes. Poultry disease is generally spread when birds ingest infectious organisms or contaminated debris, soil, food or drinking water in the dung. The features of the disease are bleeding, accumulation of blood in the cecum, bleeding into the dung, weakness and impaired digestion. The disease often results in death of the animal, and chickens that have healed from serious infections have significantly reduced market value due to infection.

The following compositions for use in growing crops and crop growing areas or for covering seeds are generally suitable for topical use on humans or animals, storage products, household goods,
It can also be used to protect real estate or the general environment as a whole. Suitable methods of using the compounds of the present invention include: spraying on leaves, fine powder, granules, mist or foam, or liquid drench as a suspension or encapsulation composition of finely divided material, For growing crops as a treatment of soil or roots with fine powder, granules, smoke or foam; for crop seeds by using the seeds covered with liquid slurry or fine powder; for arthropods, parasites or protozoa Parenteral, oral or topical use of compositions in which the active ingredient has a rapid and / or long-term action, such as food or suitable orally ingestible pharmaceutical formulations, edible baits, salt for licking,
Add arthropods, parasites or protozoa by incorporation into supplements, pour-on formulas, sprays, baths, dips, showers, jets, fine powders, greases, shampoos, creams, wax smears or livestock self-treatment systems. To humans or animals exposed to, or exposed to, its spread; as sprays, mists, fine powders, smoke, wax smears, lacquers, granules or baits, in general environmental or storage products, wood, household goods, or household or industrial Drops in specific places where pests, including utility structures, are lurking or in waterways, wells, reservoirs or other running or spilled water; feed to livestock to control fly larvae that eat livestock dung .

In practice, the compounds of the invention will most often be part of a composition. These compositions can be used to control arthropods, especially insects or mites; nematodes; or parasitic or protozoan pests. The composition may be of any type known in the art suitable for use on the desired pest in any building, indoors or outdoors, or on vertebrates by internal or external administration. These compositions comprise, as active ingredient, at least one compound of the invention as described above, for example, an agriculturally or pharmaceutically acceptable solid or liquid carrier or diluent, auxiliary, surfactant, suitable for the intended use. Etc. together with one or more other miscible components. These compositions can be prepared by methods known in the art and are also part of the present invention.

These compositions comprise a protective colloid, an adhesive,
Thickening agents, thixotropic agents, penetrants, spray oils (especially for the use of mites), stabilizers, preservatives (especially mold preservatives), sequestering agents, etc., and insecticide properties (especially insecticides) , Acaricidal, nematicidal or fungicidal properties) or other known active ingredients having plant growth regulating properties. More generally, the compounds used according to the invention can be combined with all solid or liquid additives which correspond to the customary methods of formulation.

Compositions suitable for agricultural, horticultural use and the like include formulations suitable for use as, for example, sprays, fine powders, granules, fogs, foams, emulsions and the like.

Compositions suitable for administration to vertebrates or humans include oral, parenteral, subcutaneous, for example, pour-o.
n) or formulations suitable for topical administration.

The compositions for oral administration comprise one or more compounds of the general formula (I) and a pharmaceutically acceptable carrier or coating, tablets, pills, capsules, pastes, gels, drenches, medicinal foods, medicament containing It includes drinking water, pharmaceutical supplements, sustained release tablets or devices for sustained release intended to be retained in the gastrointestinal tract. Any of these can contain the active ingredient contained in microcapsules, or coated with an acid or alkali resistant or other pharmaceutically acceptable enteric coating. Feed premixes or concentrates containing the compounds of the present invention for use in the production of pharmaceutical-containing food, drinking water or other substances for consumption by animals can also be used.

Compositions for parenteral administration include solutions, emulsions or suspensions in any suitable pharmaceutically acceptable vehicles or subcutaneous solid or semi-solids designed to release the active ingredient over an extended period of time. It contains implants or pellets and can be manufactured and sterilized by any suitable method known in the art.

Compositions for subcutaneous and topical administration include sprays, fine powders, baths, dips, showers, jets, greases, shampoos, creams, wax smears or pour-on formulations or devices (eg, topical or systemic arthropods). Ear tags, which are applied to the animal outside the body in such a way as to exterminate it.

Solid or liquid baits suitable for the control of arthropods include carriers containing one or more compounds of general formula (I) and a food substance or certain other substance which facilitates their uptake by the arthropod. Consists of a diluent.

The effective dose of the compounds used in the present invention can vary widely depending, inter alia, on the nature of the pest to be eliminated or, for example, on the extent to which these pests infest the crop. Generally, the compositions of the present invention comprise from about 0.05% to about 95% by weight of one or more active ingredients of the present invention, from about 1% to about 95% by weight of one or more solid or liquid carriers, and Optionally, from about 0.1% to about 50% by weight of one or more other miscible components, such as surfactants.

[0231] As used herein, the term "carrier" refers to
Represents organic or inorganic natural or synthetic ingredients which, when combined with the active ingredient, facilitate the application of the active ingredient to, for example, plants, seeds or soil. Accordingly, the carrier must generally be inert and acceptable (eg, agriculturally acceptable, especially to the plants being treated).

The carrier may be a solid such as clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer (eg ammonium salt), a natural mineral of earth such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, bentonite Or it may be diatomaceous earth, or a synthetic mineral of earth, such as silica, alumina or silicates, especially aluminum silicate or magnesium silicate. Suitable solid carriers for granules are the following: ground or fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite; synthetic granules of inorganic or organic powder; organic substances such as sawdust, coconut Husks, corn cobs, corn husks or tobacco stalk granules; diatomaceous earth, tricalcium phosphate, powdered cork or adsorbent carbon black; water-soluble polymers, resins, waxes; or solid fertilizers. Such a solid composition may optionally contain one or more miscible wetting agents, dispersing agents, emulsifying agents or coloring agents, which when solid also function as diluents.

The carrier may be a liquid, for example, water; alcohol, especially butanol or glycol and its ethers or esters, especially methyl glycol acetate; ketones, especially acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; Hydrogen or especially xylene or alkyl naphthalene; mineral or vegetable oil; aliphatic chlorinated hydrocarbons especially trichloroethane or methylene chloride; aromatic chlorinated hydrocarbons especially chlorobenzene; water-soluble or very polar solvents such as dimethylformamide;
Dimethyl sulfoxide or N-methylpyrrolidone; liquefied gas or the like or a mixture thereof.

The surfactant may be an ionic or nonionic emulsifier, dispersant or wetting agent or a mixture of such surfactants. These include, for example, salts of polyacrylic acid, salts of lignosulfonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty esters or fatty amines, substituted phenols ( Especially alkyl phenols or aryl phenols), sulfosuccinate salts, taurine derivatives (especially alkyl taurates), alcohol or ethylene oxide / phenol polycondensate phosphoric acid esters, fatty acid and polyol esters, sulfuric acid, sulfonic acid or There are phosphoric acid functional derivatives. When the active ingredient and / or the inert carrier is completely or slightly soluble in water and the carrier of the composition for use is water, the presence of at least one surfactant is generally required.

The composition of the present invention may further contain additives such as an adhesive or a coloring agent. Adhesives such as carboxymethylcellulose or natural or synthetic polymers in the form of powders, granules or lattices, such as gum arabic, polyvinyl alcohol or polyvinyl acetate, natural phospholipids such as cephalin or lecithin, or synthetic phospholipids can be used in the formulation. . Coloring agents such as inorganic dyes such as iron oxide, titanium oxide or Persian blue; organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes; salts of micronutrients such as iron, magnesium, boron, copper, cobalt, molybdenum or zinc can also be used.

Compositions containing compounds of general formula (I) which can be used for the control of arthropod, plant nematodes, parasites or protozoan pests include synergists (eg piperonyl butoxide or sesamex), stabilizing substances, Other insecticides, acaricides, plant nematocides, anthelmintics or coccidioides, fungicides (suitable for agricultural or veterinary use, such as benomyl and iprodione), fungicides, arthropods or vertebrae It may also contain animal attractants or insect repellents or pheromones, deodorants, fragrances, dyes or adjuvant therapeutics such as trace elements. These can be devised to improve the strength, persistence, safety, uptake at the desired site, the spectrum of the pest to control, or to perform other useful functions of the composition in the animal or location to be treated.

Examples of other pesticidally active compounds which may be included in or used with the composition according to the invention are: acephate, chloropyrifos, demeton-S-methyl, disulfotone, etoprofos ,
Fenitrothion, fenamiphos, phonofos, isazofos, isofenphos, malathion, monocrotofos, parathion, folate, fosalon, pirimifos-methyl, terbufos, triazofos, cyfluthrin, cypamethrin, deltamethrin, fenpropasulin, fenvalerate, permethrin, teflucarbal Sulfane, methomyl, oxamyl, pirimicarb, benziocarb, teflubenzuron, dicofol, endosulfan, lindane, benzoxime, cartap, cyhexatin, tetradiphon, avermectin, ivermectin, milbemycin, thiophanate, trichlorfon, dichlorphos, diaveridine or dimetriadazole.

Thus, for agricultural use of the compositions, the compounds of formula (I) will generally be in the form of a composition, which may take the form of various solids or liquids.

The solid forms of the compositions which can be used are dusting powders (content of compound of formula (I) up to 80%), wettable powders or granules (including water-dispersible granules), in particular extruded, compressed, Obtained by injecting into granules carrier or granulating starting from powder (the content of the compound of formula (I) in these hydratable powders or granules is from about 0.5% to about 80% There is). . Solid, homogeneous or heterogeneous compositions containing one or more compounds of general formula (I), such as granules, pellets, briquettes or capsules, can be used to treat accumulated water or running water over an extended period of time. A similar effect can be obtained using the drop-wise or intermittent feeding of the water-dispersible concentrate described herein.

Liquid compositions include, for example, aqueous or non-aqueous solutions or suspensions (eg, emulsifiable concentrates, emulsions, flowables, dispersions or solutions) or aerosols. The liquid composition is in particular emulsified in the form of a liquid or a composition adapted to form a liquid composition when used, for example in the form of an aqueous spray or mist (including those of low or very low volume) or an aerosol. Also included are thickeners, dispersions, emulsions, flowables, aerosols, wettable powders (or sprayable powders), dry flowables or pastes.

Liquid compositions, for example in the form of emulsifiable or soluble concentrates, most often contain from about 5% to about 80% by weight of active ingredient, but in the case of emulsions or solutions in ready-to-use form About 0.01% to about 2 active ingredients
It contains 0%. The emulsifiable or soluble thickener may also contain, in addition to the solvent, from about 2 to about 50% of suitable additives, such as stabilizers, surfactants, penetrants, preservatives, coloring agents or tackifiers, if necessary. For example, emulsions of any desired concentration particularly suitable for use on plants can be obtained by diluting these thickeners with water. These compositions fall within the scope of compositions that can be used in the present invention. Emulsions may be of the water-in-oil or oil-in-water type and may be concentrated.

The liquid compositions of the present invention may be used in general agricultural applications as well as, for example, on substances or locations with or with arthropods (or other pests that can be controlled with the compounds of the present invention).
E.g. buildings, outdoor or indoor storage or processing places,
It can be used for the treatment of containers or equipment or pool or running water.

All of these aqueous dispersions or emulsions or spray mixtures can be prepared, for example, by any suitable means, mainly by spraying, from about 100 to about 1,2 per hectare.
It can be used on crops in the proportion of 00 liters of spray mixture. This percentage can be higher or lower (eg, low volume or ultra low volume) depending on the needs and usage. The compounds or compositions of the present invention can be advantageously used on plants, especially roots or leaves, from which pests are to be removed. Another use of the compounds or compositions of the present invention is by chemigation, ie, by adding a formulation containing the active ingredient to the irrigation water. Sprinkler irrigation may be used for leaf insecticidal, and surface or subsurface irrigation for soil or systemic pesticides.

The concentrated suspension that can be used by spraying is
Does not precipitate (finely ground), usually about 10% by weight of active ingredient
About 75% by weight, surfactant about 0.5% to about 30% by weight, thixotropic agent about 0.1% to about 10% by weight,
Suitable additives, such as antifoams, preservatives, stabilizers, penetrants, adhesives, from about 0% to about 30% by weight and stable including water or organic liquids in which the active ingredient is poorly or not soluble at all. Manufacture to make a fluid. Some organic solid or inorganic salts can be dissolved in the carrier to prevent precipitation or to act as an anticoagulant for water.

The wettable powder (or powder for spraying) is usually
About 10% to about 80% by weight of active ingredient, about 20% solid carrier
% To about 90% by weight, about 0% to about 5% by weight wetting agent, about 3% to about 10% by weight dispersing agent and optionally one or more stabilizers and / or other additives. For example, about 0% by weight to about 80% by weight of a penetrant, an adhesive, an anti-solidification agent, a coloring agent, and the like.
Produced to contain% by weight. To obtain these hydratable powders, the active ingredient is thoroughly mixed with a substance capable of impregnating the porous filler in a suitable mixer and ground in a mill or other suitable mill. Thereby, a hydratable powder having excellent hydration ability and suspension ability can be obtained. Suspension of this in water gives any desired concentration, which suspension can be used very advantageously, especially for application to the leaves of plants.

"Water-dispersible granules (WG)" (granules readily dispersible in water) include compositions that are substantially similar to hydratable powders. This involves contacting the formulation described for the wettable powder with a wet process (contacting the finely divided active ingredient with an inert filler and a small amount of water, for example 1% -20% by weight, or with an aqueous solution of a dispersant or binder). After contact, dewatering and sieving) or granulation by a dry method (compression, then crushing and sieving) can be used.

The amount of active ingredient (effective amount) used in the formulated composition is generally about 0.005 to about 15 kg / ha,
Preferably it is about 0.01 to about 2 kg / ha. Accordingly, the proportions and concentrations of the formulated compositions will vary with the use or the nature of the composition and the use of the composition. In general, compositions used to control arthropod, plant nematodes, parasites or protozoan pests usually contain from about 0.00001% to about 9% by weight.
5% by weight, more specifically about 0.0005% by weight to about 5%
0% by weight of one or more compounds of the general formula (I) or the whole active ingredient (ie the compound of the general formula (I) and other substances toxic to arthropods or plant nematodes, anthelmintics, Anticoccidial agents, synergists, trace elements or stabilizers). The actual composition used and the percentage of use will be chosen by the farmer, livestock producer, physician or veterinarian, pest control or practitioner to achieve the desired effect.

Solid or liquid compositions for topical use in animals, wood, stored products or household products usually have a composition of about 0.00000.
5% to about 90% by weight, more specifically about 0.001%
% By weight-contains about 10% by weight of one or more compounds of general formula (I). For administering solid or liquid compositions to animals parenterally, including orally or subcutaneously, they will usually contain from about 0.1% to about 90% by weight of one or more compounds of general formula (I). Contains. Medicinal feeds usually contain from about 0.001% to about 3% by weight of one or more compounds of general formula (I). Concentrates or supplements to be mixed with the feed usually contain from about 5% to about 90% by weight, preferably from about 5% to about 50% by weight, of one or more compounds of the general formula (I). Mineral salts usually contain from about 0.1% to about 10% by weight of a compound of general formula (I).

Fine powder or liquid compositions for use in livestock, humans, objects, buildings or outdoor areas may comprise from about 0.0001% to about 15% by weight, more specifically from about 0.005% to about 15% by weight. It contains 2.0% by weight of one or more compounds of the general formula (I). The preferred concentration in the treated water is about 0.0001
ppm-about 20 ppm, more specifically about 0.001 p
pm-contains about 5.0 ppm of one or more compounds of general formula (I) and can be used for treatment in fish farms with a suitable exposure time. The bait may contain about 0.01% to about 5%, preferably about 0.01% to about 1.0% by weight of one or more compounds of general formula (I).

When administered parenterally, orally or subcutaneously or otherwise to a vertebrate, the dose of the compound of general formula (I) will depend on the species, age or health of the vertebrate and the arthropod,
It will vary depending on the nature and extent of the actual or potential infestation of the parasite or protozoan pest. About 0.1 to about 100 mg, preferably about 2.0 to about 2 mg / kg of animal body weight
A single dose of 0.0 mg, or about 0.01 to about 20.0 mg / kg of animal body weight per day for continuous dosing,
Preferably about 0.1 to about 5.0 mg is generally suitable for oral or parenteral administration. Using a sustained release formulation or device, the animal can be administered in a single dose with the required daily dose over several months.

The following compositions, Examples 29A-29L, are compounds of general formula (I), especially compounds of general formula (II), for use in arthropods, especially mites or insects, plant nematodes or parasites or protozoan pests. ) Compound, for example, Preparation Example 1
27. The composition of claim 27. Example 29A-2
By diluting each of the compositions described in 9F with water, a spray composition having a concentration suitable for use in fields can be obtained. The general chemical description of the components used in the following exemplified compositions Examples 29A-29L is as follows (all percentages below are by weight): Trade name Chemical description Ethylan BCP Nonylphenol Ethylene oxide condensation Soprophor BSU Tristyrylphenol ethylene oxide condensate Arylan CA 70% w / v solution of calcium dodecylbenzenesulfonate Solvesso 150 Light C ₁₀ aromatic solvent Arylan S Sodium dodecylbenzenesulfonate Darvan No2 Sodium lignosulfonate Celite magnesium silicate silicate Carrier Sopropon T36 Sodium salt of polycarboxylic acid Rhodigel 23 Polysaccharide xanthan gum Bentone 38 Organic induction of montmorillonite magnesium Conductor Aerosil Very fine silicon dioxide Example 29A Produce a water-soluble concentrate with the following composition: Active ingredient 7% Ethylan BCP 10% N-methylpyrrolidone 83% Ethylan dissolved in part of N-methylpyrrolidone
The active ingredient is added to the BCP solution with heating and stirring until dissolved. The resulting solution is made up to volume with the remaining solvent.

Example 29B An emulsifiable concentrate (EC) is prepared with the following composition: Active ingredient 7% Soprophor BSU 4% Arylan CA 4% N-methylpyrrolidone 50% Solvesso 150 35% The first three ingredients are N Dissolve in methylpyrrolidone, then add Solvesso 150 to final volume.

Example 29C A hydratable powder (WP) is produced with the following composition: Active ingredient 40% Arylan S 2% Darvan No2 5% Celite PF 53% The ingredients are mixed and ground with a hammer mill to obtain granules Powder less than 50 microns.

Example 29D An aqueous Flowab1e formulation is prepared with the following composition: Active ingredient 40.00% Ethylane BCP 1.00% Sopropon T360 0.20% Ethylene glycol 5.00% Rhodigel 230 0.15 % Water 53.65% Ingredients are mixed well and ground in a bead mill until an average particle size of less than 3 microns is obtained.

Example 29E An emulsifiable suspension concentrate is prepared with the following composition: Active ingredient 30.0% Ethylane BCP 10.0% Bentone 38 0.5% Solvesso 150 59.5% The ingredients are mixed well. Grind in a bead mill until an average particle size of less than 3 microns is obtained.

Example 29F A water-dispersible granule is prepared with the following composition: Active ingredient 30% Darvan No2 15% Alylan S 8% Celite PF 47% The ingredients are mixed, pulverized with a flow energy mill and then (10) %) And granulate on a rotary pelletizer. The resulting granules are dewatered in a fluid bed dryer to remove excess water.

Example 29G Spray powder is prepared with the following composition: Active ingredient 1-10% Talc powder (ultrafine) 99-90% Ingredients are mixed well and, if necessary, further ground to give a fine powder. I do. This powder can be used on arthropod infestation sites, such as garbage dumps, storage products, household items or animals where the arthropod is infested or at risk, to control the arthropod by ingestion. it can. Suitable means for distributing the dusting powder to arthropod infestations include mechanical blowers, handshakers or livestock self-treatment devices.

Example 29H Poison bait is prepared with the following composition: Active ingredient 0.1-1.0% Flour 80% Molasses 19.9-19% Ingredients are mixed well and optionally in the form of a bait . This bait can be used, for example, in arthropods such as ants, grasshoppers, cockroaches, or home or industrial buildings with flies, such as kitchens,
Distribute to hospitals or stores, outdoor areas and control arthropods by ingestion.

Example 29I A solution formulation is prepared with the following composition: Active ingredient 15% Dimethyl sulfoxide 85% The active ingredient is dissolved in dimethyl sulfoxide with mixing or heating as needed. This solution is sterilized by transcutaneous pour-on application on livestock with arthropods or by filtration through a polytetrafluoroethylene membrane (pore size 0.22 μm), followed by a solution of 1.2 per 100 kg of animal body weight.
It is injected parenterally at a rate of -12 ml.

Example 29J A hydratable powder is prepared with the following composition: Active ingredient 50% Ethylane BCP 5% Aerosil 5% Celite PF 40% Ethylan BCP is adsorbed on Aerosil and then mixed with other ingredients, Grind with a hammer mill to obtain a hydratable powder. 0.001% by weight of active ingredient-2
Livestock diluted with water to a concentration of% by weight and sprayed on arthropods such as larvae of the order Diptera or plant nematodes, or with or at risk of arthropods, parasites or protozoa Spray or dipping (dippin
g) or orally from drinking water to control arthropods, parasites or protozoa.

Example 29K If desired, a sustained release tablet composition is formed from granules containing the following components in various percentages (similar to the preceding composition): Active ingredient Density agent Slow Release agent Binder The well-mixed ingredients are granulated and compressed into tablets having a specific gravity of 2 or more. It can be orally administered to ruminant livestock and retained in the rumen, releasing the active ingredient slowly and continuously over a long period of time, and can eliminate arthropods, parasites or protozoa on ruminant livestock. .

Example 29L Sustained-release compositions in the form of granules, pellets, briquettes, etc. are prepared with the following composition: Active ingredient 0.5-25% Polyvinyl chloride 75-99.5% Dioctyl phthalate (plastic Agent) Catalyst amount After mixing the components, melt extrusion or molding into a suitable shape. These compositions are, for example, added to pool water,
It can be processed into collars or ear tags for livestock and used to control pests by sustained release.

While the invention has been described in detail with specific and descriptive details and preferred specific examples have been described, without departing from the scope and spirit of the invention as defined in the appended claims.
Modifications, variations, or changes apparent to one of ordinary skill in the art will be readily made.

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──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Gale Scottton Powell, United States, North Carolina 27606, Raleigh, Bakersfield Drive 6508 (72) Inventor Michael Thomas Pilate, United States of America, North Carolina -27606, Rori, Brent Road-805 (72) Inventor David T. Way Chiyou, United States of America, North Carolina-27615, Roli, Danutz Day Drive 400 (72) Inventor, Jiamin Juan United States of America, North Carolina, 27514, Chapel Hill, Overland Drive 409 (58) Fields studied (Int. Cl. ⁷ , DB name) C07D 401/04 A01N 43/56 CA (STN) CAOLD ( STN) REGISTRY (STN)

Claims (25)

(57) [Claims] 1. The following formula (I): Wherein X represents halogen, nitro or unsubstituted or halo-substituted alkylsulfenyl, alkylsulfinyl or alkylsulfonyl, wherein the alkyl moiety has 1 to 1 carbon atoms.
4 is a straight or branched chain, and when substituted, is substituted to the extent that the alkyl moiety is completely substituted with one or more halogen atoms that are the same or different from each other; and Y is hydrogen, Halogen, cyano, alkylsulfenyl,
Alkylsulfinyl, alkylsulfonyl, alkoxy, amino, alkylamino, dialkylamino, trialkylammonium salt, cyanoalkylamino, alkoxyalkylamino, alkoxycarbonylamino,
Represents alkylcarbonylamino, haloalkylcarbonylamino, alkylaminocarbonylamino, dialkylaminocarbonylamino or alkoxyalkylideneimino, wherein the alkyl and alkoxy moieties have 1 carbon atom
4 is a straight or branched chain, wherein the haloalkyl moiety is substituted to the extent that the alkyl moiety is completely substituted with one or more halogen atoms that are the same or different from each other, and Z is cyano or halogen. , R ₂ , R ₃ , R ₄ and R ₅ each independently represent hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano or nitro, wherein the alkyl and alkoxy moieties are straight-chain having 1 to 4 carbon atoms. Or a branched chain, wherein the halo-substituted moiety is substituted to the extent that the alkyl and alkoxy moieties are completely substituted with one or more halogen atoms that are the same or different from each other, and at least one of R _{2 to} R ₅ Are other than hydrogen].
-Pyridyl) pyrazole or an acid addition salt thereof. 2. The following formula (II): [Wherein, Y represents the meaning defined in claim 1, and R ₁ is a carbon atom having 1 or more carbon atoms substituted with one or more halogen atoms that are the same or different from each other until the alkyl group is completely substituted. Represents 4 straight-chain or branched alkyl, n is 0, 1 or 2; R ₂ and R ₄ have the meanings defined in claim 1 with the proviso that R
_At least one of R ₂ and R ₄ is other than hydrogen], or an acid addition salt thereof. (3) wherein Y is amino, alkylamino, alkylsulfenyl,
Represents an alkylsulfinyl, an alkylsulfonyl, an alkoxyalkylamino, an alkylcarbonylamino, a haloalkylcarbonylamino or an alkoxyalkylideneimino, wherein the alkyl and alkoxy portions are linear or branched having 1 to 4 carbon atoms, and the haloalkyl portions are the same as each other. Or R ₂ is hydrogen or halogen; R ₄ is hydrogen, halogen, haloalkyl or haloalkoxy; haloalkyl Or the haloalkoxy moiety is a straight or branched chain having 1 to 4 carbon atoms, and is substituted by one or more halogen atoms that are the same or different from each other to the extent that the alkyl and alkoxy moieties are completely substituted. At least one of _{R 2} and _{R 4} A compound according to claim 2 is other than hydrogen. Wherein Y is amino, alkylamino, alkoxymethylamino or alkoxyalkylideneimino, the alkyl and alkoxy moieties contain one or two carbon atoms, and R ₁ is trifluoromethyl, dichlorofluoromethyl Or a chlorodifluoromethyl, wherein R ₂ is bromine, chlorine or fluorine, and R ₄ is bromine, chlorine, fluorine, trifluoromethyl or trifluoromethoxy. 5. 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4
1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-chlorodifluoromethylsulfinylpyrazole; 1- [2- (3 -Chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-chlorodifluoromethylsulfonylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino -3-cyano-4-dichlorofluoromethylsulfenylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-ethoxymethylamino-3-cyano-4
-Dichlorofluoromethylsulfenylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-trifluoromethylsulfenylpyrazole; 1- [2- ( 3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-trifluoromethylsulfinylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5- Amino-3-cyano-4-trifluoromethylsulfonylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-difluoromethylsulfinylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-dichlorophenyl 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-methylsulphenylpyrazole; 1- [2- (3-chloro-5) -Trifluoromethyl) pyridyl] -5-amino-3-cyano-4-methylsulfinylpyrazole; or 1- [2- (3,5-dichloro) pyridyl] -5-amino-3-cyano-4-trifluoro The compound according to claim 4, which is methylsulfenylpyrazole; or an acid addition salt thereof. 6. 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4
1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-chlorodifluoromethylsulfonylpyrazole; 1- [2- (3- Chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-trifluoromethylsulfinylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino- 3-cyano-4-trifluoromethylsulfonylpyrazole; 1- [2- (3-chloro-5-trifluoromethyl) pyridyl] -5-amino-3-cyano-4-difluoromethylsulfinylpyrazole; or 1- [ 2- (3
-Chloro-5-trifluoromethyl) pyridyl] -5-
The compound according to claim 5, which is amino-3-cyano-4-methylsulfinylpyrazole; or an acid addition salt thereof. 7. One or more agricultures comprising an effective amount of a compound of formula (I) or an acid addition salt thereof as active ingredient, comprising one or more solid or liquid carriers, diluents, adjuvants and / or surfactants. A composition for controlling arthropods, nematodes, parasites or protozoan pests, comprising together with a target or a pharmaceutically compatible ingredient , provided that
The composition that is not applied to the subject . 8. The composition according to claim 7 , comprising 0.05 to 95% by weight of the compound of the formula (I) or an acid addition salt thereof. 9. 1-95% by weight of a solid or liquid carrier 0.1 to 50 wt% of diluent, the composition according to claim 7 or 8 comprising an adjuvant and surface active agent. 10. A method for controlling arthropods, nematodes, parasites or protozoan pests in a certain place other than human, comprising the steps of: providing an effective amount of a compound of the formula (I) or a compound thereof. A method comprising treating with an acid addition salt. 11. The location is an agricultural or horticultural plant or a medium in which the plant grows, the pest is an arthropod or nematode pest of the plant, and the treatment is a plant or the plant. 11. The method according to claim 10 , comprising applying to the growing medium an effective amount of a compound of formula (I) or an acid addition salt thereof. 12. The compound of the formula (I) or an acid addition salt thereof is applied at a rate of 0.005 kg to 15 kg per hectare of treated area to a place where arthropod or nematode pests are to be controlled. Item 12. The method according to Item 11 . 13. A compound of formula (I) or an acid addition salt thereof
Claim applied at 0.01kg ~2kg / ha 1
3. The method according to 2 . 14. The pest is a tick, aphid, insect or plant nematode or a combination thereof, wherein the compound is contained in the soil in which the plant is planted or to be planted, or the plant seed, the plant seed, 13. The method of claim 12 , comprising applying the compound to roots or plant leaves.
Or the method of 13 . 15. The insect according to claim 15, wherein the insect is a soil insect of the order Coleoptera, Lepidoptera or Diptera or a leaf insect of the order Lepidoptera, Coleoptera, Homoptera or Alloptera. A
The method according to claim 14 , wherein the aphid belongs to the order Homoptera. 16. Use according to the arthropod, parasite or protozoan parasitizing inside or outside a non-human warm - blooded vertebrate in the field of veterinary or livestock raising or for maintaining public health. 11. The method according to 10 . 17. The following formula 4 : [Wherein, R represents C _1-4 alkyl, and R ₂ , R ₃ , R
₄ and R ₅ represent the meaning defined in claim 1]. 18. The following formula 5 : [Wherein, R represents C _1-4 alkyl, and R ₁ represents C _1-4
Alkyl or C _1-4 haloalkyl; R ₂ ,
R ₃ , R ₄ and R ₅ represent the meaning defined in claim 1]
A compound represented by the formula: 19. The following formula 6 : [Wherein, R ₁ represents C _1-4 alkyl or C _1-4 haloalkyl, and R ₂ , R ₃ , R ₄ and R ₅ have the meanings defined in claim 1]. 20. The following formula 9 : [Wherein R ₂ , R ₃ , R ₄ and R ₅ represent the meaning defined in Claim 1]. 21. The following formula 10 : [Wherein R ₂ , R ₃ , R ₄ and R ₅ represent the meaning as defined in the claims]. 22. The following formula 11 : [Wherein, R represents C _1-4 alkyl, and R ₂ , R ₃ , R
₄ and R ₅ have the meaning as defined in claim 1 and X is halogen or nitro. 23. The following formula 12 : Wherein X is halogen or nitro, and R ₂ , R ₃ ,
R ₄ and R ₅ represent the meaning defined in claim 1]. 24. The following formula (V): [Wherein, Y, Z, R ₂ , R ₃ , R ₄ and R ₅ are claims 1
Which represents the meaning defined in [1]. 25. Y is amino, alkylamino, alkoxymethylamino or alkoxyalkylideneimino; the alkyl and alkoxy moieties contain one or two carbon atoms; R ₂ is bromine, chlorine or fluorine;
₃ and R ₅ are each hydrogen, R ₄ is bromine, chlorine, fluorine, a compound according to any one of claims 17-24 trifluoromethyl or trifluoromethoxy.